Positive resist composition for immersion exposure and pattern forming method

ABSTRACT

A positive resist composition for immersion exposure includes the following (A) to (D): (A) a resin capable of decomposing by an action of an acid to increase a solubility of the resin in an alkali developer; (B) a compound capable of generating an acid upon irradiation with an actinic ray or radiation; (C) a resin having at least either one of a fluorine atom and a silicon atom; and (D) a mixed solvent containing at least one kind of a solvent selected from the group consisting of solvents represented by any one of the following formulae (S1) to (S3) as defined in the specification, in which a total amount of the at least one kind of the solvent is from 3 to 20 mass % based on all solvents of the mixed solvent (D).

This is a Continuation Application of U.S. application Ser. No.13/057,287, filed Feb. 3, 2011; which is a U.S. National Stage Entry ofPCT/JP2009/067192 filed Sep. 25, 2009, which claims priority under 35U.S.C. §119 from Japanese Application No. 2008-249216 filed Sep. 26,2008, and from Japanese Application No. 2009-219717, filed Sep. 24,2009, the contents of all of which are incorporated herein by reference.

TECHNICAL FIELD

The present invention relates to a positive resist composition forimmersion exposure, which is used in the process of producing asemiconductor such as IC, in the production of a circuit board forliquid crystal, thermal head and the like, and in the lithographyprocess of other photo-applications, and a pattern forming method usingthe same. More specifically, the present invention relates to a positiveresist composition for immersion exposure, which is suitable forexposure by an immersion projection exposure apparatus using a lightsource that emits far ultraviolet light at a wavelength of 300 nm orless, and a pattern forming method using the same.

BACKGROUND ART

Along with the miniaturization of a semiconductor device, the trend ismoving into shorter wavelength of the exposure light source and highernumerical aperture (high NA) of the projection lens. At present, anexposure machine with NA of 0.84 has been developed, where an ArFexcimer laser having a wavelength of 193 nm is used as the light source.As commonly well known, these factors can be expressed by the followingformulae:(Resolution)=k ₁·(λ/NA)(Depth of focus)=±k ₂·λ/NA²wherein λ is the wavelength of the exposure light source, NA is thenumerical aperture of the projection lens, and k₁ and k₂ arecoefficients related to the process.

For more shortening the wavelength and thereby obtaining higherresolution, a so-called immersion method of filling a highrefractive-index liquid (hereinafter sometimes referred to as an“immersion liquid”) between the projection lens and the sample has beenconventionally known as a technique for raising the resolution in anoptical microscope.

As for the “effect of immersion”, assuming that NA₀=sin θ, theabove-described resolution and depth of focus in the immersion can beexpressed by the following formulae:(Resolution)=k ₁·(λ₀ /n)/NA₀(Depth of focus)=±k ₂·(λ₀ /n)/NA₀ ²wherein λ₀ is the wavelength of exposure light in air, n is therefractive index of the immersion liquid based on air, and θ is theconvergence half-angle of beam.

That is, the effect of immersion is equal to use of an exposurewavelength of 1/n. In other words, in the case of a projection opticalsystem with the same NA, the depth of focus can be made n times largerby the immersion. This is effective for all pattern profiles and can becombined with the super-resolution technology under study at present,such as phase-shift method and modified illumination method.

An example of the apparatus where immersion exposure is applied to thetransfer of a fine image pattern of a semiconductor device is describedin JP-A-7-220990 (the term “JP-A” as used herein means an “unexaminedpublished Japanese patent application”) and the like.

The latest technical progress of immersion exposure is reported, forexample, in Proc. SPIE, Vol. 4688, page 11 (2002), J. Vac. Sci.Technol., B, 17 (1999) and Proc. SPIE, Vol. 3999, page 2 (2000). In thecase of using an ArF excimer laser as the light source, pure water(refractive index at 193 nm: 1.44) is considered to be most promising asthe immersion liquid in view of safety in handling as well as thetransmittance and refractive index at 193 nm.

With the advent of a resist for a KrF excimer laser (248 nm), an imageforming method called chemical amplification is used as the imageforming method for a resist so as to compensate for the reduction insensitivity due to light absorption. To explain the image-forming methodof positive chemical amplification by example, this is an image formingmethod of exposing a resist to decompose an acid generator in theexposed area to thereby generate an acid, utilizing the generated acidas the reactive catalyst to change an alkali-insoluble group to analkali-soluble group by the bake after exposure (PEB: Post ExposureBake), and removing the exposed area by alkali development.

A resist for an ArF excimer laser (wavelength: 193 nm) using thischemical amplification mechanism is becoming predominant at present.

In the immersion exposure process, when exposure is performed using ascan-type immersion exposure machine, unless the immersion liquid movesfollowing the movement of lens, the exposure speed decreases and thismay affect the productivity. For this reason, it is preferred that theresist film has a high receding angle for the immersion liquid.

In JP-A-2006-048029, International Publication No. 07/116,664,JP-A-2008-65098, it is indicated that the resist film surface can behydrophobed by adding a specific resin or the like.

SUMMARY OF INVENTION

In the immersion exposure, a circular defect called watermark issometimes produced due to the action of a water droplet remaining on theresist film after exposure.

An object of the present invention is to provide a positive resistcomposition for immersion exposure, ensuring that the receding contactangle for immersion liquid at the immersion exposure can be moreimproved and the watermark defect can be reduced, and a pattern formingmethod using the same.

As a result of intensive studies to attain the above-described object,the present inventors have accomplished the present invention.

(1) A positive resist composition for immersion exposure, comprising thefollowing (A) to (D):

(A) a resin capable of decomposing by an action of an acid to increase asolubility of the resin in an alkali developer;

(B) a compound capable of generating an acid upon irradiation with anactinic ray or radiation;

(C) a resin having at least either one of a fluorine atom and a siliconatom; and

(D) a mixed solvent containing at least one kind of a solvent selectedfrom the group consisting of solvents represented by any one of thefollowing formulae (S1) to (S3), in which a total amount of the at leastone kind of the solvent is from 3 to 20 mass % based on all solvents ofthe mixed solvent (D):

wherein each of R₁ to R₇ independently represents an alkyl group, acycloalkyl group or an aryl group; and

R₁ and R₂, R₃ and R₄, and R₆ and R₇ may combine with each other to forma ring, respectively.

(2) The positive resist composition for immersion exposure as describedin (1) above,

wherein the resin (C) has at least one group represented by any one ofthe following formulae (F2) to (F4) and (CS-1) to (CS-3):

wherein each of R₅₇ to R₆₈ independently represents a hydrogen atom, afluorine atom, an alkyl group, a cycloalkyl group or an aryl group,provided that at least one of R₅₇ to R₆₁, at least one of R₆₂ to R₆₄ andat least one of R₆₅ to R₆₈ each represent a fluorine atom or an alkyl,cycloalkyl or aryl group with at least one hydrogen atom beingsubstituted by a fluorine atom; and

R₆₂ and R₆₃ may combine with each other to form a ring:

wherein each of R₁₂ to R₂₆ independently represents an alkyl group or acycloalkyl group;

each of L₃ to L₅ independently represents a single bond or a divalentlinking group; and

n represents an integer of 1 to 5.

(3) The positive resist composition for immersion exposure as describedin (2) above,

wherein the resin (C) contains at least one repeating unit derived froman acrylate or methacrylate having a group represented by any one offormulae (F2) to (F4) and (CS-1) to (CS-3).

(4) The positive resist composition for immersion exposure as describedin any one of (1) to (3) above,

wherein the total amount of the at least one kind of the solventselected from the group consisting of solvents represented by any one offormulae (S1) to (S3) is from 3 to 10 mass % based on all solvents ofthe mixed solvent (D).

(5) The positive resist composition for immersion exposure as describedin any one of (1) to (4) above, the mixed solvent (D) contains at leastone kind of a solvent selected from the group consisting of solventsrepresented by any one of formulae (S1) and (S2).

(6) The positive resist composition for immersion exposure as describedin any one of (1) to (5) above,

wherein the mixed solvent (D) contains a solvent having an alkylenecarbonate structure as the at least one kind of the solvent selectedfrom the group consisting of solvents represented by any one of formulae(S1) to (S3).

(7) The positive resist composition for immersion exposure as describedin any one of (1) to (6) above,

wherein the mixed solvent (D) contains a solvent having a lactonestructure as the at least one kind of the solvent selected from thegroup consisting of solvents represented by any one of formulae (S1) to(S3).

(8) The positive resist composition for immersion exposure as describedin any one of (1) to (7) above,

wherein the mixed solvent (D) contains a hydroxyl group-containingsolvent, a hydroxyl group-free solvent and the at least one kind of thesolvent selected from the group consisting of solvents represented byany one of formulae (S1) to (S3).

(9) The positive resist composition for immersion exposure as describedin any one of (1) to (8) above,

wherein the mixed solvent (D) contains an alkylene glycol monoalkylether acetate, an alkylene glycol monoalkyl ether and the at least onekind of the solvent selected from the group consisting of solventsrepresented by any one of formulae (S1) to (S3).

(10) A pattern forming method, comprising:

-   -   forming a resist film from the positive resist composition for        immersion exposure as described in any one of (1) to (9) above;

exposing the resist film through an immersion liquid so as to form anexposed resist film; and

developing the exposed resist film.

DESCRIPTION OF EMBODIMENTS

[1] (A) Resin Capable of Increasing the Solubility in an AlkaliDeveloper by the Action of an Acid

The resist composition of the present invention contains (A) a resincapable of increasing the solubility in an alkali developer by theaction of an acid.

The resin capable of increasing the solubility in an alkali developer bythe action of an acid (acid-decomposable resin) has a group capable ofdecomposing by the action of an acid to produce an alkali-soluble group(hereinafter sometimes referred to as an “acid-decomposable group”), inthe main or side chain of the resin or in both the main chain and theside chain.

The resin (A) is preferably insoluble or sparingly soluble in an alkalideveloper.

The acid-decomposable group preferably has a structure where analkali-soluble group is protected by a group capable of decomposing andleaving by the action of an acid.

Examples of the alkali-soluble group include a phenolic hydroxyl group,a carboxyl group, a fluorinated alcohol group, a sulfonic acid group, asulfonamide group, a sulfonylimide group, an(alkylsulfonyl)(alkylcarbonyl)methylene group, an(alkylsulfonyl)(alkylcarbonyl)imide group, a bis(alkylcarbonyl)methylenegroup, a bis(alkylcarbonyl)imide group, a bis(alkylsulfonyl)methylenegroup, a bis(alkylsulfonyl)imide group, a tris(alkylcarbonyl)methylenegroup and a tris(alkylsulfonyl)methylene group.

Preferred alkali-soluble groups are a carboxyl group, a fluorinatedalcohol group (preferably hexafluoroisopropanol) and a sulfonic acidgroup.

The group preferred as the acid-decomposable group is a group where ahydrogen atom of such an alkali-soluble group is substituted by a groupcapable of leaving by the action of an acid.

Examples of the group capable of leaving by the action of an acidinclude —C(R₃₆)(R₃₇)(R₃₈), —C(R₃₆)(R₃₇)(OR₃₉) and —C(R₀₁)(R₀₂)(OR₃₉).

In the formulae, each of R₃₆ to R₃₉ independently represents an alkylgroup, a cycloalkyl group, an aryl group, an aralkyl group or an alkenylgroup, and R₃₆ and R₃₇ may combine with each other to form a ring.

Each of R₀₁ and R₀₂ independently represents a hydrogen atom, an alkylgroup, a cycloalkyl group, an aryl group, an aralkyl group or an alkenylgroup.

The acid-decomposable group is preferably, for example, a cumyl estergroup, an enol ester group, an acetal ester group or a tertiary alkylester group, more preferably a tertiary alkyl ester group.

The acid-decomposable group-containing repeating unit which can becontained in the resin (A) is preferably a repeating unit represented bythe following formula (AI):

In formula (AI), Xa₁ represents a hydrogen atom, a methyl group whichmay have a substituent or a group represented by —CH₂—R₉. R₉ representsa hydroxyl group or a monovalent organic group. As the monovalentorganic group, for example, an alkyl group having a carbon number of 5or less or an acyl group is exemplified, and an alkyl group having acarbon number of 3 or less is preferred, and a methyl group is morepreferred. Xa₁ is preferably a hydrogen atom, a methyl group, atrifluoromethyl group or a hydroxymethyl group.

T represents a single bond or a divalent linking group.

Each of Rx₁, Rx₂ and Rx₃ independently represents an alkyl group (linearor branched) or a cycloalkyl group (monocyclic or polycyclic).

Rx₂ and Rx₃ may combine to form a cycloalkyl group (monocyclic orpolycyclic).

Examples of the divalent linking group of T includes an alkylene group,a —COO-Rt- group and a —O-Rt- group, wherein Rt represents an alkylenegroup or a cycloalkylene group.

T is preferably a single bond or a —COO-Rt- group. Rt is preferably analkylene group having a carbon number of 1 to 5, more preferably a —CH₂—group or a —(CH₂)₃— group.

The alkyl group of Rx₁ to Rx₃ is preferably an alkyl group having acarbon number of 1 to 4, such as methyl group, ethyl group, n-propylgroup, isopropyl group, n-butyl group, isobutyl group and tert-butylgroup.

The cycloalkyl group of Rx₁ to Rx₃ is preferably a monocyclic cycloalkylgroup such as cyclopentyl group and cyclohexyl group, or a polycycliccycloalkyl group such as norbornyl group, tetracyclodecanyl group,tetracyclododecanyl group and adamantyl group.

The cycloalkyl group formed by combining Rx₂ and Rx₃ is preferably amonocyclic cycloalkyl group such as cyclopentyl group and cyclohexylgroup, or a polycyclic cycloalkyl group such as norbornyl group,tetracyclodecanyl group, tetracyclododecanyl group and adamantyl group.

An embodiment where Rx₁ is a methyl group or an ethyl group and Rx₂ andRx₃ are combined to form the above-described cycloalkyl group ispreferred.

Each of the groups above may have a substituent, and examples of thesubstituent include an alkyl group (having a carbon number of 1 to 4), ahalogen atom, a hydroxyl group, an alkoxy group (having a carbon numberof 1 to 4), a carboxyl group and an alkoxycarbonyl group (having acarbon number of 2 to 6). The carbon number is preferably 8 or less.

The content in total of the acid-decomposable group-containing repeatingunits is preferably from 20 to 70 mol %, more preferably from 30 to 50mol %, based on all repeating units in the resin.

Specific preferred examples of the repeating unit having anacid-decomposable group are set forth below, but the present inventionis not limited thereto.

In specific examples, each of Rx and Xa₁ represents a hydrogen atom,CH₃, CF₃ or CH₂OH, and each of Rxa and Rxb represents an alkyl grouphaving a carbon number of 1 to 4. Z represents, when a plurality of Z'sare present, each independently represents, a substituent containing apolar group. Specific examples of the substituent containing a polargroup are the same as those for R₁₀ in formula (2-1) described later. prepresents 0 or a positive integer.

The resin (A) is more preferably a resin having, as the repeating unitrepresented by formula (AI), at least either one of a repeating unitrepresented by formula (1) and a repeating unit represented by formula(2).

In formulae (1) and (2), each of R₁ and R₃ independently represents ahydrogen atom, a methyl group or a group represented by —CH₂—R₉. R₉represents a monovalent organic group, and the specific examples thereofare the same as those of R₉ regarding formula (AI) described above.

Each of R₂, R₄, R₅ and R₆ independently represents an alkyl group or acycloalkyl group.

Each R independently represents an atomic group necessary for forming analicyclic structure together with the carbon atom.

R₁ is preferably a hydrogen atom, a methyl group, a trifluoromethylgroup or a hydroxymethyl group.

The alkyl group in R₂ may be linear or branched and may have asubstituent.

The cycloalkyl group in R₂ may be monocyclic or polycyclic and may havea substituent.

R₂ is preferably an alkyl group, more preferably an alkyl group having acarbon number of 1 to 10, still more preferably an alkyl group having acarbon number of 1 to 5, and examples thereof include a methyl group andan ethyl group.

Each R independently represents an atomic group necessary for forming analicyclic structure together with the carbon atom. The alicyclicstructure formed by R and the carbon atom is preferably a monocyclicalicyclic structure, and the carbon number thereof is preferably from 3to 7, more preferably 5 or 6.

R₃ is preferably a hydrogen atom or a methyl group, more preferably amethyl group.

The alkyl group in R₄, R₅ and R₆ may be linear or branched and may havea substituent. The alkyl group is preferably an alkyl group having acarbon number of 1 to 4, such as methyl group, ethyl group, n-propylgroup, isopropyl group, n-butyl group, isobutyl group and tert-butylgroup.

The cycloalkyl group in R₄, R₅ and R₆ may be monocyclic or polycyclicand may have a substituent. The cycloalkyl group is preferably amonocyclic cycloalkyl group such as cyclopentyl group and cyclohexylgroup, or a polycyclic cycloalkyl group such as norbornyl group,tetracyclodecanyl group, tetracyclododecanyl group and adamantyl group.

The repeating unit represented by formula (1) includes a repeating unitrepresented by the following formula (1-a). In the formula, R₁ and R₂have the same meanings as in formula (1).

The repeating unit represented by formula (2) is preferably a repeatingunit represented by the following formula (2-1):

In formula (2-1), R₃ to R₅ have the same meanings as in formula (2).

R₁₀ represents a polar group-containing substituent. In the case where aplurality of R₁₀'s are present, each R₁₀ may be the same as or differentfrom every other R₁₀. The polar group-containing substituent is, forexample, a linear or branched alkyl group or cycloalkyl group having ahydroxyl group, a cyano group, an amino group, an alkylamide group or asulfonamide group, preferably an alkyl group having a hydroxyl group,more preferably an alkyl group (preferably having a carbon number of 3to 5) having a tertiary carbon atom to which the hydroxyl group issubstituted, and still more preferably —C(CH₃)₂OH. As for the branchedalkyl group, an isopropyl group is particularly preferred.

p represents an integer of 0 to 1.5. p is preferably an integer of 0 to2, more preferably 0 or 1.

The resin (A) may contain a plurality of repeating units each having anacid-decomposable group.

The resin (A) is preferably a resin containing, as the repeating unitrepresented by formula (AI), a repeating unit represented by formula (1)and a repeating unit represented by formula (2). In another embodiment,a resin containing at least two kinds of repeating units represented byformula (1) as the repeating unit represented by formula (AI) ispreferred.

In the case where the resin (A) contains a plurality ofacid-decomposable group-containing repeating units or where the resin(A) and after-mentioned resin (A′) have different acid-decomposablegroup-containing repeating units, preferred examples of the combinationare set forth below. In the following formulae, each R independentlyrepresents a hydrogen atom or a methyl group.

The resin (A) preferably contains a repeating unit having a lactonegroup.

As for the lactone group, any group may be used as long as it has alactone structure, but the lactone structure is preferably a 5- to7-membered ring lactone structure, and a structure where another ringstructure is condensed to the 5- to 7-membered ring lactone structure inthe form of forming a bicyclo or spiro structure is preferred. The resinmore preferably contains a repeating unit having a lactone structurerepresented by any one of the following formulae (LC1-1) to (LC1-16).The lactone structure may be bonded directly to the main chain. Amongthese lactone structures, preferred are (LC1-1), (LC1-4), (LC1-5),(LC1-6), (LC1-13) and (LC1-14). By virtue of using a specific lactonestructure, LWR and development defect are improved.

The lactone structure moiety may or may not have a substituent (Rb₂).Preferred examples of the substituent (Rb₂) include an alkyl grouphaving a carbon number of 1 to 8, a cycloalkyl group having a carbonnumber of 4 to 7, an alkoxy group having a carbon number of 1 to 8, analkoxycarbonyl group having a carbon number of 2 to 8, a carboxyl group,a halogen atom, a hydroxyl group, a cyano group and an acid-decomposablegroup. Among these, an alkyl group having a carbon number of 1 to 4, acyano group and an acid-decomposable group are more preferred. n₂represents an integer of 0 to 4. When n₂ is an integer of 2 or more,each substituent (Rb₂) may be the same as or different from every othersubstituent (Rb₂) and also, the plurality of substituents (Rb₂) maycombine with each other to form a ring.

As for the repeating unit having a lactone structure, a repeating unitrepresented by the following formula (AII) is also preferred.

In formula (AII), Rb₀ represents a hydrogen atom, a halogen atom or analkyl group having a carbon number of 1 to 4. Preferred examples of thesubstituent which the alkyl group of Rb₀ may have include a hydroxylgroup and a halogen atom. The halogen atom of Rb₀ includes a fluorineatom, a chlorine atom, a bromine atom and an iodine atom. Rb₀ ispreferably a hydrogen atom, a methyl group, a hydroxymethyl group or atrifluoromethyl group, more preferably a hydrogen atom or a methylgroup.

Ab represents a single bond, an alkylene group, a divalent linking grouphaving a monocyclic or polycyclic alicyclic hydrocarbon structure, anether group, an ester group, a carbonyl group, or a divalent groupcomprising a combination thereof, and is preferably a single bond or adivalent linking group represented by -Ab₁-CO₂—.

Ab₁ represents a linear or branched alkylene group or a monocyclic orpolycyclic cycloalkylene group and is preferably a methylene group, anethylene group, a cyclohexylene group, an adamantylene group or anorbornylene group.

V represents a group having a structure represented by any one offormulae (LC1-1) to (LC1-16).

Specific examples of the repeating unit having a lactone group are setforth below, but the present invention is not limited thereto.

(In the formulae, Rx is H, CH₃, CH₂OH or CF₃.)

(In the formulae, Rx is H, CH₃, CH₂OH or CF₃.)

(In the formulae, Rx is H, CH₃, CH₂OH or CF₃.)

The repeating unit having a particularly preferred lactone groupincludes the repeating units shown below. By selecting an optimallactone group, the pattern profile and the iso/dense bias are improved.

(In the formulae, Rx is H, CH₃, CH₂OH or CF₃.)

The resin (A) preferably contains a lactone structure-containingrepeating unit represented by the following formula (3):

In formula (3), A represents an ester bond (a group represented by—COO—), or a group represented by —CONH—.

R₀ represents, in the case where a plurality of R₀'s are present, eachindependently represents, an alkylene group, a cycloalkylene group or acombination thereof.

Z represents, in the case where a plurality of Z's are present, eachindependently represents, an ether bond, an ester bond, an amide bond, aurethane bond or a urea bond.

R₈ represents a monovalent organic group having a lactone structure.

n is a repetition number of the structure represented by —R₀—Z— in therepeating unit represented by formula (3) and represents an integer of 1to 5.

R₇ represents a hydrogen atom, a halogen atom or an alkyl group.

Each of the alkylene group and the cyclic alkylene group of R₀ may havea substituent.

Z is preferably an ether bond or an ester bond, more preferably an esterbond.

The alkyl group of R₇ is preferably an alkyl group having a carbonnumber of 1 to 4, more preferably a methyl group or an ethyl group,still more preferably a methyl group. The alkyl group in R₇ may besubstituted, and examples of the substituent include a halogen atom suchas fluorine atom, chlorine atom and bromine atom, mercapto group,hydroxy group, an alkoxy group such as methoxy group, ethoxy group,isopropoxy group, tert-butoxy group and benzyloxy group, and an acetoxygroup such as acetyloxy group and propionyloxy group. R₇ is preferably ahydrogen atom, a methyl group, a trifluoromethyl group or ahydroxymethyl group.

The chain alkylene group in R₀ is preferably a chain alkylene grouphaving a carbon number of 1 to 10, more preferably from 1 to 5, andexamples thereof include a methylene group, an ethylene group and apropylene group. The cyclic alkylene group is preferably a cyclicalkylene having a carbon number of 3 to 20, and examples thereof includecyclohexylene, cyclopentylene, norbornylene and adamantylene. Forrealizing the effects of the present invention, a chain alkylene groupis more preferred.

The lactone structure-containing substituent represented by R₈ is notlimited as long as it has a lactone structure. Specific examples thereofinclude lactone structures represented by formulae (LC1-1) to (LC1-16)and of these, a structure represented by (LC1-4) is preferred.Structures where n₂ in (LC1-1) to (LC1-16) is an integer of 2 or lessare more preferred.

Also, R₈ is more preferably a monovalent organic group containing alactone structure (cyanolactone) having a cyano group as thesubstituent.

Specific examples of the repeating unit containing a group having alactone structure represented by formula (3) are set forth below, butthe present invention is not limited thereto.

In the following specific examples, R is a hydrogen atom, an alkyl groupwhich may have a substituent, or a halogen atom, preferably a hydrogenatom, a methyl group, or a hydroxymethyl or acetoxymethyl group which isan alkyl group having a substituent.

The repeating unit having a lactone structure is more preferably arepeating unit represented by the following formula (3-1):

In formula (3-1), R₇, A, R₀, Z and n have the same meanings as informula (3).

R₉ represents, when a plurality of R₉'s are present, each independentlyrepresents, an alkyl group, a cycloalkyl group, an alkoxycarbonyl group,a cyano group, a hydroxyl group or an alkoxy group, and when a pluralityof R₉'s are present, two members thereof may form a ring.

X represents an alkylene group, an oxygen atom or a sulfur atom.

n represents an integer of 1 to 5.

m is the number of substituents and represents an integer of 0 to 5. mis preferably 0 or 1.

The alkyl group of R₉ is preferably an alkyl group having a carbonnumber of 1 to 4, more preferably a methyl group or an ethyl group, andmost preferably a methyl group. The cycloalkyl group may be acyclopropyl, cyclobutyl, cyclopentyl or cyclohexyl group. Examples ofthe ester group include a methoxycarbonyl group, an ethoxycarbonylgroup, an n-butoxycarbonyl group and a tert-butoxycarbonyl group.Examples of the substituent include a hydroxy group, an alkoxy groupsuch as methoxy group and ethoxy group, a cyano group, and a halogenatom such as fluorine atom. R₉ is preferably a cyano group.

Examples of the alkylene group of X include a methylene group and anethylene group.

X is preferably an oxygen atom or a methylene group.

When m≧1, at least one R₉ is preferably substituted at the α- orβ-position, more preferably at the α-position, of the carbonyl group ofthe lactone.

Specific examples of the lactone structure-containing repeating unitrepresented by formula (3-1) are set forth below, but the presentinvention is not limited thereto. In the following specific examples, Ris a hydrogen atom, an alkyl group which may have a substituent, or ahalogen atom, preferably a hydrogen atom, a methyl group, or ahydroxymethyl or acetoxymethyl group which is an alkyl group having asubstituent.

A plurality of repeating units represented by formula (3) may becombined. In this case, a combination of two or more repeating unitswhere n=0, a combination of two or more repeating units where n=1, and acombination of a repeating unit where n=0 and a repeating unit where n=1are preferred.

The repeating unit having a lactone structure usually has an opticalisomer, but any optical isomer may be used. One optical isomer may beused alone or a mixture of a plurality of optical isomers may be used.In the case of mainly using one optical isomer, the optical purity (ee)thereof is preferably 90 or more, more preferably 95 or more.

The content of the repeating unit having a lactone group is preferablyfrom 15 to 60 mol %, more preferably from 20 to 50 mol %, still morepreferably from 30 to 50 mol %, based on all repeating units in theresin.

The resin (A) preferably contains a repeating unit having a hydroxylgroup or a cyano group, in addition to repeating units represented byformula (AI) and formula (AII). Thanks to this repeating unit, theadherence to substrate and the affinity for developer are enhanced. Therepeating unit having a hydroxyl group or a cyano group is preferably arepeating unit having an alicyclic hydrocarbon structure substituted bya hydroxyl group or a cyano group, and is preferably a repeating unitnot having an acid decomposable group. The alicyclic hydrocarbonstructure in the alicyclic hydrocarbon structure substituted by ahydroxyl group or a cyano group is preferably an adamantyl group, adiamantyl group or a norbornane group. The alicyclic hydrocarbonstructure substituted by a hydroxyl group or a cyano group is preferablya partial structure represented by any one of the following formulae(VIIa) to (VIId):

In formulae (VIIa) to (VIIc), each of R₂c to R₄c independentlyrepresents a hydrogen atom, a hydroxyl group or a cyano group, providedthat at least one of R₂c to R₄c represents a hydroxyl group or a cyanogroup. A structure where one or two members out of R₂c to R₄c are ahydroxyl group with the remaining being a hydrogen atom is preferred. Informula (VIIa), it is more preferred that two members out of R₂c to R₄care a hydroxyl group and the remaining is a hydrogen atom.

The repeating unit having a partial structure represented by any one offormulae (VIIa) to (VIId) includes repeating units represented by thefollowing formulae (AIIa) to (AIId):

In formulae (AIIa) to (AIId), R₁c represents a hydrogen atom, a methylgroup, a trifluoromethyl group or a hydroxymethyl group.

R₂c to R₄c have the same meanings as R₂c to R₄c in formulae (VIIa) to(VIII).

The content of the repeating unit having a hydroxyl group or a cyanogroup is preferably from 5 to 40 mol %, more preferably from 5 to 30 mol%, still more preferably from 10 to 25 mol %, based on all repeatingunits in the resin (A).

Specific examples of the repeating unit having a hydroxyl group or acyano group are set forth below, but the present invention is notlimited thereto.

The resin for use in the positive resist composition for immersionexposure of the present invention may contain a repeating unit having analkali-soluble group. The alkali-soluble group includes a carboxylgroup, a sulfonamide group, a sulfonylimide group, a bisulfonylimidegroup, and an aliphatic alcohol with the α-position being substituted byan electron-withdrawing group, such as hexafluoroisopropanol group. Arepeating unit having a carboxyl group is more preferred. By virtue ofcontaining the repeating unit having an alkali-soluble group, theresolution increases in the usage of forming contact holes. As for therepeating unit having an alkali-soluble group, all of a repeating unitwhere an alkali-soluble group is directly bonded to the resin mainchain, such as repeating unit by an acrylic acid or a methacrylic acid,a repeating unit where an alkali-soluble group is bonded to the resinmain chain through a linking group, and a repeating unit where analkali-soluble group is introduced into the polymer chain terminal byusing an alkali-soluble group-containing polymerization initiator orchain transfer agent at the polymerization, are preferred. The linkinggroup may have a monocyclic or polycyclic cyclohydrocarbon structure. Inparticular, a repeating unit by an acrylic acid or a methacrylic acid ispreferred.

The content of the repeating unit having an alkali-soluble group ispreferably from 0 to 20 mol %, more preferably from 3 to 15 mol %, stillmore preferably from 5 to 10 mol %, based on all repeating units in theresin (A).

Specific examples of the repeating unit having an alkali-soluble groupare set forth below, but the present invention is not limited thereto.

(In the formulae, Rx is H, CH₃, CF₃ or CH₂OH.)

The resin (A) for use in the present invention may further contain arepeating unit having a polar group-free alicyclic hydrocarbon structureand not exhibiting acid decomposability. Thanks to this repeating unit,the dissolving out of low molecular components from the resist film tothe immersion liquid at the immersion exposure can be reduced. Thisrepeating unit includes a repeating unit represented by formula (4):

In formula (4), R₅ represents a hydrocarbon group having at least onecyclic structure and having neither a hydroxyl group nor a cyano group.

Ra represents a hydrogen atom, an alkyl group or a —CH₂—O—Ra₂ group,wherein Ra₂ represents a hydrogen atom, an alkyl group or an acyl group.Ra is preferably a hydrogen atom, a methyl group, a hydroxymethyl groupor a trifluoromethyl group, more preferably a hydrogen atom or a methylgroup.

The cyclic structure possessed by R₅ includes a monocyclic hydrocarbongroup and a polycyclic hydrocarbon group. Examples of the monocyclichydrocarbon group include a cycloalkyl group having a carbon number of 3to 12, such as cyclopentyl group, cyclohexyl group, cycloheptyl groupand cyclooctyl group, and a cycloalkenyl group having a carbon number of3 to 12, such as cyclohexenyl group. The monocyclic hydrocarbon group ispreferably a monocyclic hydrocarbon group having a carbon number of 3 to7, more preferably a cyclopentyl group or a cyclohexyl group.

The polycyclic hydrocarbon group includes a ring gathered hydrocarbongroup and a crosslinked cyclic hydrocarbon group. Examples of the ringgathered hydrocarbon group include a bicyclohexyl group and aperhydronaphthalenyl group. Examples of the crosslinked hydrocarbon ringinclude bicyclic hydrocarbon ring such as pinane ring, bornane ring,norpinane ring, norbornane ring and bicyclooctane ring (e.g.,bicyclo[2.2.2]octane ring, bicyclo[3.2.1]octane ring), a tricyclichydrocarbon ring such as homobledane ring, adamantane ring,tricyclo[5.2.1.0^(2,6)]decane ring and tricyclo[4.3.1.1^(2,5)]undecanering, and a tetracyclic hydrocarbon ring such astetracyclo[4.4.0.1^(2,5).1^(7,10)]dodecane ring andperhydro-1,4-methano-5,8-methanonaphthalene ring. The crosslinked cyclichydrocarbon ring also includes a condensed cyclic hydrocarbon ring, forexample, a condensed ring formed by condensing a plurality of 5- to8-membered cycloalkane rings, such as perhydronaphthalene (decalin)ring, perhydroanthracene ring, perhydrophenathrene ring,perhydroacenaphthene ring, perhydrofluorene ring, perhydroindene ringand perhydrophenalene ring.

Preferred examples of the crosslinked cyclic hydrocarbon ring include anorbornyl group, an adamantyl group, a bicyclooctanyl group and atricyclo[5,2,1,0^(2,6)]decanyl group. Of these crosslinked cyclichydrocarbon rings, a norbornyl group and an adamantyl group are morepreferred.

Such an alicyclic hydrocarbon group may have a substituent, andpreferred examples of the substituent include a halogen atom, an alkylgroup, a hydroxyl group protected by a protective group, and an aminogroup protected by a protective group. The halogen atom is preferablybromine atom, chlorine atom or fluorine atom, and the alkyl group ispreferably a methyl group, an ethyl group, a butyl group or a tert-butylgroup. This alkyl group may further have a substituent, and thesubstituent which the alkyl group may further have includes a halogenatom, an alkyl group, a hydroxyl group protected by a protective group,and an amino group protected by a protective group.

Examples of the protective group include an alkyl group, a cycloalkylgroup, an aralkyl group, a substituted methyl group, a substituted ethylgroup, an alkoxycarbonyl group and an aralkyloxycarbonyl group. Thealkyl group is preferably an alkyl group having a carbon number of 1 to4, the substituted methyl group is preferably a methoxymethyl group, amethoxythiomethyl group, a benzyloxymethyl group, a tert-butoxymethylgroup or a 2-methoxyethoxymethyl group, the substituted ethyl group ispreferably a 1-ethoxyethyl group or a 1-methyl-1-methoxyethyl group, theacyl group is preferably an aliphatic acyl group having a carbon numberof 1 to 6, such as formyl group, acetyl group, propionyl group, butyrylgroup, isobutyryl group, valeryl group and pivaloyl group, and thealkoxycarbonyl group is preferably an alkoxycarbonyl group having acarbon number of 2 to 4.

The content of the repeating unit having a polar group-free alicyclichydrocarbon structure and not exhibiting acid decomposability ispreferably from 0 to 40 mol %, more preferably from 0 to 20 mol %, basedon all repeating units in the resin (A).

Specific examples of the repeating unit having a polar group-freealicyclic hydrocarbon structure and not exhibiting acid decomposabilityare set forth below, but the present invention is not limited thereto.In the formulae, Ra represents H, CH₃, CH₂OH or CF₃.

The resin for use in the positive resist composition for immersionexposure of the present invention may contain, in addition to theabove-described repeating structural units, various repeating structuralunits for the purpose of controlling the dry etching resistance,suitability for standard developer, adherence to substrate, resistprofile and properties generally required of the resist, such asresolution, heat resistance and sensitivity.

Examples of such a repeating structural unit include, but are notlimited to, repeating structural units corresponding to the monomersdescribed below.

Thanks to such a repeating structural unit, the performance required ofthe resin for use in the positive resist composition for immersionexposure of the present invention, particularly,

(1) solubility in coating solvent,

(2) film-forming property (glass transition point),

(3) alkali developability,

(4) film loss (selection of hydrophilic, hydrophobic or alkali-solublegroup),

(5) adherence of unexposed area to substrate,

(6) dry etching resistance and the like, can be subtly controlled.

Examples of the monomer include a compound having oneaddition-polymerizable unsaturated bond selected from acrylic acidesters, methacrylic acid esters, acrylamides, methacrylamides, allylcompounds, vinyl ethers and vinyl esters.

Other than these, an addition-polymerizable unsaturated compoundcopolymerizable with the monomers corresponding to the above-describedvarious repeating structural units may be copolymerized.

In the resin (A) for use in the positive resist composition forimmersion exposure of the present invention, the molar ratio ofrespective repeating structural units contained is appropriatelydetermined to control the dry etching resistance of resist, suitabilityfor standard developer, adherence to substrate, resist profile andperformances generally required of the resist, such as resolution, heatresistance and sensitivity.

In the case where the positive resist composition for immersion exposureof the present invention is used for ArF exposure, the resin (A) for usein the positive resist composition for immersion exposure of the presentinvention preferably has no aromatic group in view of transparency toArF light.

Also, the resin (A) preferably contains no fluorine atom and no siliconatom in view of compatibility with (C) a resin having at least either afluorine atom or a silicon atom, which is described later.

The resin (A) for use in the positive resist composition for immersionexposure of the present invention is preferably a resin where allrepeating units are composed of a (meth)acrylate-based repeating unit.In this case, all repeating units may be a methacrylate-based repeatingunit, all repeating units may be an acrylate-based repeating unit, orall repeating unit may comprise a methacrylate-based repeating unit andan acrylate-based repeating unit, but the content of the acrylate-basedrepeating unit is preferably 50 mol % or less based on all repeatingunits. The resin is more preferably a copolymerized polymer containingfrom 20 to 50 mol % of an acid decomposable group-containing(meth)acrylate-based repeating unit, from 20 to 50 mol % of a lactonegroup-containing (meth)acrylate-based repeating unit, from 5 to 30 mol %of a (meth)acrylate-based repeating unit having an alicyclic hydrocarbonstructure substituted by a hydroxyl group or a cyano group, and from 0to 20 mol % of other (meth)acrylate-based repeating units.

In the case where the positive resist composition for immersion exposureof the present invention is irradiated with KrF excimer laser light,electron beam, X-ray or high-energy beam at a wavelength of 50 nm orless (e.g., EUV), the resin (A) preferably further contains ahydroxystyrene-based repeating unit, more preferably ahydroxystyrene-based repeating unit, a hydroxystyrene-based repeatingunit protected by an acid-decomposable group, and an acid-decomposablerepeating unit such as tertiary alkyl(meth)acrylate.

Preferred examples of the hydroxystyrene-based repeating unit having anacid-decomposable group include a repeating unit composed of atert-butoxycarbonyloxystyrene, a 1-alkoxyethoxystyrene or a tertiaryalkyl(meth)acrylate. A repeating unit composed of a2-alkyl-2-adamantyl(meth)acrylate or adialkyl(1-adamantyl)methyl(meth)acrylate is more preferred.

The resin (A) for use in the present invention can be synthesized by anordinary method (for example, radical polymerization). Examples of thesynthesis method in general include a batch polymerization method ofdissolving monomer species and an initiator in a solvent and heating thesolution, thereby effecting the polymerization, and a droppingpolymerization method of adding dropwise a solution containing monomerspecies and an initiator to a heated solvent over 1 to 10 hours. Adropping polymerization method is preferred. Examples of the reactionsolvent include tetrahydrofuran, 1,4-dioxane, ethers such as diisopropylether, ketones such as methyl ethyl ketone and methyl isobutyl ketone,an ester solvent such as ethyl acetate, an amide solvent such asdimethylformamide and dimethylacetamide, and a solvent capable ofdissolving the composition of the present invention, which is describedlater, such as propylene glycol monomethyl ether acetate, propyleneglycol monomethyl ether and cyclohexanone. The polymerization is morepreferably performed using the same solvent as the solvent used in thepositive resist composition for immersion exposure of the presentinvention. By the use of this solvent, production of particles duringstorage can be suppressed.

The polymerization reaction is preferably performed in an inert gasatmosphere such as nitrogen or argon. As for the polymerizationinitiator, the polymerization is initiated using a commerciallyavailable radical initiator (e.g., azo-based initiator, peroxide). Theradical initiator is preferably an azo-based initiator, and an azo-basedinitiator having an ester group, a cyano group or a carboxyl group ispreferred. Preferred examples of the initiator includeazobisisobutyronitrile, azobisdimethylvaleronitrile and dimethyl2,2′-azobis(2-methylpropionate). The initiator is added additionally orin parts, if desired. After the completion of reaction, the reactionproduct is charged into a solvent, and the desired polymer is recoveredby a method such as powder or solid recovery. The reaction concentrationis from 5 to 50 mass %, preferably from 10 to 30 mass %, and thereaction temperature is usually from 10 to 150° C., preferably from 30to 120° C., more preferably from 60 to 100° C. (In this specification,mass ratio is equal to weight ratio.)

The weight average molecular weight of the resin (A) for use in thepresent invention is preferably from 1,000 to 200,000, more preferablyfrom 2,000 to 20,000, still more preferably from 3,000 to 15,000, yetstill more preferably from 3,000 to 10,000, in terms of polystyrene bythe GPC method. When the weight average molecular weight is from 1,000to 200,000, the heat resistance, dry etching resistance anddevelopability can be prevented from deterioration and also, thefilm-forming property can be prevented from deteriorating due to highviscosity.

The polydispersity (molecular weight distribution) is usually from 1 to3, preferably from 1 to 2.6, more preferably from 1 to 2, still morepreferably from 1.4 to 2.0. As the molecular weight distribution issmaller, the resolution and resist profile are more excellent, the sidewall of the resist pattern is smoother, and the property in terms ofroughness is more improved.

In the positive resist composition for immersion exposure of the presentinvention, the amount of the resin (A) blended in the entire compositionis, in the case where the composition contains the following resin (A′),as a total amount of resins (A) and (A), preferably from 50 to 99.9 mass%, more preferably from 60 to 99.0 mass %, based on the entire solidcontent.

Resin (A′):

In the positive resist composition for immersion exposure of the presentinvention, two or more kinds of resins (A) may be contained, forexample, an acid-decomposable resin (A′) different from the resin (A)may be used in combination with the resin (A).

The acid-decomposable resin (A′) is not particularly limited as long asit is different from the resin (A), and, for example, a knownacid-decomposable resin may also be used.

The resin (A′) may contain the repeating unit represented by formula(AI), the repeating unit having a lactone group described above, therepeating unit represented by formula (4), and the like.

As for the resin (A) and the resin (A′), there may be included, forexample, a case where the kind of the repeating unit having anacid-decomposable group is different from that in the resin (A) (forexample, a case where the resin (A) contains the repeating unitrepresented by formula (1) and the resin (A′) contains the repeatingunit represented by formula (2) or where the resin (A) contains therepeating unit represented by formula (1) and the resin (A′) containsthe repeating unit represented by formula (1) that is different from therepeating unit represented by formula (1) contained in the resin (A)), acase where the resin (A) has a lactone group and the resin (A′) does nothave a lactone group, a case where the kind of the lactone group isdifferent between the resin (A) and the resin (A′), a case where theresin (A) contains the repeating unit represented by formula (4) and theresin (A′) does not contain the repeating unit represented by formula(4), and a case where the kind of the repeating unit represented byformula (4) is different between the resin (A) and the resin (A′).

The content of the resin (A′) is preferably from 0.1 to 10 times bymass, more preferably from 0.5 to 2 times by mass, based on the resin(A).

Incidentally, a resin other than the resin (A), the resin (A′) and theresin (C) described later may be used in combination within the rangenot impairing the effects of the present invention.

[2] (B) Compound Capable of Generating an Acid Upon Irradiation with anActinic Ray or Radiation

The positive photosensitive composition for immersion exposure of thepresent invention contains a compound capable of generating an acid uponirradiation with an actinic ray or radiation (hereinafter sometimesreferred to as an “acid generator”).

The acid generator which can be used may be appropriately selected froma photo-initiator for cationic photopolymerization, a photo-initiatorfor radical photopolymerization, a photo-decoloring agent for dyes, aphoto-discoloring agent, a compound known to generate an acid uponirradiation with an actinic ray or radiation and used for microresist orthe like, and a mixture thereof.

Examples of such an acid generator include a diazonium salt, aphosphonium salt, a sulfonium salt, an iodonium salt, imidosulfonate,oxime sulfonate, diazodisulfone, disulfone and o-nitrobenzyl sulfonate.

Also, a compound where a group or compound capable of generating an acidupon irradiation with an actinic ray or radiation is introduced into themain or side chain of a polymer, for example, compounds described inU.S. Pat. No. 3,849,137, German Patent 3,914,407, JP-A-63-26653,JP-A-55-164824, JP-A-62-69263, JP-A-63-146038, JP-A-63-163452,JP-A-62-153853 and JP-A-63-146029, may be used.

Furthermore, compounds capable of generating an acid by the effect oflight described, for example, in U.S. Pat. No. 3,779,778 and EuropeanPatent 126,712 may also be used.

Out of the acid generators, compounds represented by the followingformulae (ZI), (ZII) and (ZIII) are preferred.

In formula (ZI), each of R₂₀₁, R₂₀₂ and R₂₀₃ independently represents anorganic group.

The number of carbons in the organic group as R₂₀₁, R₂₀₂ and R₂₀₃ isgenerally from 1 to 30, preferably from 1 to 20.

Two members out of R₂₀₁ to R₂₀₃ may combine to form a ring structure,and the ring may contain an oxygen atom, a sulfur atom, an ester bond,an amide bond or a carbonyl group. Examples of the group formed bycombining two members out of R₂₀₁ to R₂₀₃ include an alkylene group(e.g., butylene, pentylene).

Z⁻ represents a non-nucleophilic anion.

Examples of the non-nucleophilic anion as Z⁻ include sulfonate anion,carboxylate anion, sulfonylimide anion, bis(alkylsulfonyl)imide anionand tris(alkylsulfonyl)methyl anion.

The non-nucleophilic anion is an anion having an extremely low abilityof causing a nucleophilic reaction and this anion can suppress thedecomposition with aging due to intramolecular nucleophilic reaction.Thanks to this anion, the aging stability of the resist is enhanced.

Examples of the sulfonate anion include an aliphatic sulfonate anion, anaromatic sulfonate anion and a camphorsulfonate anion.

Examples of the carboxylate anion include an aliphatic carboxylateanion, an aromatic carboxylate anion and an aralkylcarboxylate anion.

The aliphatic moiety in the aliphatic sulfonate anion may be an alkylgroup or a cycloalkyl group but is preferably an alkyl group having acarbon number of 1 to 30 or a cycloalkyl group having a carbon number of3 to 30, and examples thereof include a methyl group, an ethyl group, apropyl group, an isopropyl group, an n-butyl group, an isobutyl group, asec-butyl group, a pentyl group, a neopentyl group, a hexyl group, aheptyl group, an octyl group, a nonyl group, a decyl group, an undecylgroup, a dodecyl group, a tridecyl group, a tetradecyl group, apentadecyl group, a hexadecyl group, a heptadecyl group, an octadecylgroup, a nonadecyl group, an eicosyl group, a cyclopropyl group, acyclopentyl group, a cyclohexyl group, an adamantyl group, a norbornylgroup and a boronyl group.

The aromatic group in the aromatic sulfonate anion is preferably an arylgroup having a carbon number of 6 to 14, and examples thereof include aphenyl group, a tolyl group and a naphthyl group.

Each of the alkyl group, cycloalkyl group and aryl group in thealiphatic sulfonate anion and aromatic sulfonate anion may have asubstituent. Examples of the substituent of the alkyl group, cycloalkylgroup and aryl group in the aliphatic sulfonate anion and aromaticsulfonate anion include a nitro group, a halogen atom (e.g., fluorine,chlorine, bromine, iodine), a carboxyl group, a hydroxyl group, an aminogroup, a cyano group, an alkoxy group (preferably having a carbon numberof 1 to 15), a cycloalkyl group (preferably having a carbon number of 3to 15), an aryl group (preferably having a carbon number of 6 to 14), analkoxycarbonyl group (preferably having a carbon number of 2 to 7), anacyl group (preferably having a carbon number of 2 to 12), analkoxycarbonyloxy group (preferably having a carbon number of 2 to 7),an alkylthio group (preferably having a carbon number of 1 to 15), analkylsulfonyl group (preferably having a carbon number of 1 to 15), analkyliminosulfonyl group (preferably having a carbon number of 2 to 15),an aryloxysulfonyl group (preferably having a carbon number of 6 to 20),an alkylaryloxysulfonyl group (preferably having a carbon number of 7 to20), a cycloalkylaryloxysulfonyl group (preferably having a carbonnumber of 10 to 20), an alkyloxyalkyloxy group (preferably having acarbon number of 5 to 20), and a cycloalkylalkyloxyalkyloxy group(preferably having a carbon number of 8 to 20). As for the aryl group orring structure in each group, examples of the substituent furtherinclude an alkyl group (preferably having a carbon number of 1 to 15).

Examples of the aliphatic moiety in the aliphatic carboxylate anioninclude the same alkyl group and cycloalkyl group as those in thealiphatic sulfonate anion.

Examples of the aromatic group in the aromatic carboxylate anion includethe same aryl group as those in the aromatic sulfonate anion.

The aralkyl group in the aralkylcarboxylate anion is preferably anaralkyl group having a carbon number of 7 to 12, and examples thereofinclude a benzyl group, a phenethyl group, a naphthylmethyl group, anaphthylethyl group and a naphthylbutyl group.

Each of the alkyl group, cycloalkyl group, aryl group and aralkyl groupin the aliphatic carboxylate anion, aromatic carboxylate anion andaralkylcarboxylate anion may have a substituent. Examples of thesubstituent of the alkyl group, cycloalkyl group, aryl group and aralkylgroup in the aliphatic carboxylate anion, aromatic carboxylate anion andaralkylcarboxylate anion include the same halogen atom, alkyl group,cycloalkyl group, alkoxy group and alkylthio group as those in thearomatic sulfonate anion.

Examples of the sulfonylimide anion include saccharin anion.

The alkyl group in the bis(alkylsulfonyl)imide anion andtris(alkylsulfonyl)methyl anion is preferably an alkyl group having acarbon number of 1 to 5, and examples thereof include a methyl group, anethyl group, a propyl group, an isopropyl group, an n-butyl group, anisobutyl group, a sec-butyl group, a pentyl group and a neopentyl group.Examples of the substituent of such an alkyl group include a halogenatom, a halogen atom-substituted alkyl group, an alkoxy group, analkylthio group, an alkyloxysulfonyl group, an aryloxysulfonyl group,and a cycloalkylaryloxysulfonyl group, with a fluorine atom-substitutedalkyl group being preferred.

Other examples of the non-nucleophilic anion include fluorinatedphosphorus, fluorinated boron and fluorinated antimony.

The non-nucleophilic anion of Z″ is preferably an aliphatic sulfonateanion substituted by a fluorine atom at the α-position of the sulfonicacid, an aromatic sulfonate anion substituted by a fluorine atom or afluorine atom-containing group, a bis(alkylsulfonyl)imide anion with thealkyl group being substituted by a fluorine atom, or atris(alkylsulfonyl)methide anion with the alkyl group being substitutedby a fluorine atom. The non-nucleophilic anion is more preferably aperfluoroaliphatic sulfonate anion having a carbon number of 4 to 8 or abenzenesulfonate anion having a fluorine atom, still more preferablynonafluorobutanesulfonate anion, perfluorooctanesulfonate anion,pentafluorobenzenesulfonate anion or3,5-bis(trifluoromethyl)benzenesulfonate anion.

Examples of the organic group as R₂₀₁, R₂₀₂ and R₂₀₃ include thecorresponding groups in the compounds (ZI-1), (ZI-2) and (ZI-3)described later.

The compound may be a compound having a plurality of structuresrepresented by formula (ZI), for example, a compound having a structurewhere at least one of R₂₀₁ to R₂₀₃ in the compound represented byformula (ZI) is bonded to at least one of R₂₀₁ to R₂₀₃ in anothercompound represented by formula (ZI).

The component (ZI) is more preferably a compound (ZI-1), (ZI-2) or(ZI-3) described below.

The compound (ZI-1) is an arylsulfonium compound where at least one ofR₂₀₁ to R₂₀₃ in formula (ZI) is an aryl group, that is, a compoundhaving arylsulfonium as the cation.

In the arylsulfonium compound, all of R₂₀₁ to R₂₀₃ may be an aryl groupor a part of R₂₀₁ to R₂₀₃ may be an aryl group with the remaining beingan alkyl group or a cycloalkyl group.

Examples of the arylsulfonium compound include a triarylsulfoniumcompound, a diarylalkylsulfonium compound, an aryldialkylsulfoniumcompound, a diarylcycloalkylsulfonium compound and anaryldicycloalkylsulfonium compound.

The aryl group in the arylsulfonium compound is preferably a phenylgroup or a naphthyl group, more preferably a phenyl group. The arylgroup may be an aryl group having a heterocyclic structure containing anoxygen atom, a nitrogen atom, a sulfur atom or the like. Examples of thearyl group having a heterocyclic structure include a pyrrole residue (agroup formed by removing one hydrogen atom from a pyrrole), a furanresidue (a group formed by removing one hydrogen atom from a furan), athiophene residue (a group formed by removing one hydrogen atom from athiophene), an indole residue (a group formed by removing one hydrogenatom from an indole), a benzofuran residue (a group formed by removingone hydrogen atom from a benzofuran) and a benzothiophene residue (agroup formed by removing one hydrogen atom from a benzothiophene). Inthe case where the arylsulfonium compound has two or more aryl groups,these two or more aryl groups may be the same or different.

The alkyl or cycloalkyl group which is present, if desired, in thearylsulfonium compound is preferably a linear or branched alkyl grouphaving a carbon number of 1 to 15 or a cycloalkyl group having a carbonnumber of 3 to 15, and examples thereof include a methyl group, an ethylgroup, a propyl group, an n-butyl group, a sec-butyl group, a tert-butylgroup, a cyclopropyl group, a cyclobutyl group and a cyclohexyl group.

Each of the aryl group, alkyl group and cycloalkyl group of R₂₀₁ to R₂₀₃may have, as the substituent, an alkyl group (for example, an alkylgroup having a carbon number of 1 to 15), a cycloalkyl group (forexample, a cycloalkyl group having a carbon number of 3 to 15), an arylgroup (for example, an aryl group having a carbon number of 6 to 14), analkoxy group (for example, an alkoxy group having a carbon number of 1to 15), a halogen atom, a hydroxyl group or a phenylthio group. Thesubstituent is preferably a linear or branched alkyl group having acarbon number of 1 to 12, a cycloalkyl group having a carbon number of 3to 12, or a linear, branched or cyclic alkoxy group having a carbonnumber of 1 to 12, more preferably an alkyl group having a carbon numberof 1 to 4, or an alkoxy group having a carbon number of 1 to 4. Thesubstituent may be substituted to any one of three members R₂₀₁ to R₂₀₃or may be substituted to all of these three members. In the case whereR₂₀₁ to R₂₀₃ are an aryl group, the substituent is preferablysubstituted at the p-position of the aryl group.

The compound (ZI-2) is described below.

The compound (ZI-2) is a compound where each of R₂₀₁ to R₂₀₃ in formula(ZI) independently represents an aromatic ring-free organic group. Thearomatic ring as used herein includes an aromatic ring containing aheteroatom.

The aromatic ring-free organic group as R₂₀₁ to R₂₀₃ has a carbon numberof generally from 1 to 30, preferably from 1 to 20.

Each of R₂₀₁ to R₂₀₃ independently represents preferably an alkyl group,a cycloalkyl group, an allyl group or a vinyl group, more preferably alinear or branched 2-oxoalkyl group, a 2-oxocycloalkyl group or analkoxycarbonylmethyl group, still more preferably a linear or branched2-oxoalkyl group.

The alkyl group and cycloalkyl group of R₂₀₁ to R₂₀₃ are preferably alinear or branched alkyl group having a carbon number of 1 to 10 (e.g.,methyl, ethyl, propyl, butyl, pentyl) and a cycloalkyl group having acarbon number of 3 to 10 (e.g., cyclopentyl, cyclohexyl, norbornyl). Thealkyl group is more preferably a 2-oxoalkyl group or analkoxycarbonylmethyl group. The cycloalkyl group is more preferably a2-oxocycloalkyl group.

The 2-oxoalkyl group may be either linear or branched and is preferablya group having >C═O at the 2-position of the above-described alkylgroup.

The 2-oxocycloalkyl group is preferably a group having >C═O at the2-position of the above-described cycloalkyl group.

The alkoxy group in the alkoxycarbonylmethyl group is preferably analkoxy group having a carbon number of 1 to 5 (e.g., methoxy, ethoxy,propoxy, butoxy, pentoxy).

Each of R₂₀₁ to R₂₀₃ may be further substituted by a halogen atom, analkoxy group (for example, an alkoxy group having a carbon number of 1to 5), a hydroxyl group, a cyano group or a nitro group.

The compound (ZI-3) is a compound represented by the following formula(ZI-3), and this is a compound having a phenacylsulfonium saltstructure.

In formula (ZI-3), each of R_(1c) to R_(5c) independently represents ahydrogen atom, an alkyl group, a cycloalkyl group, an alkoxy group or ahalogen atom.

Each of R_(6c) and R_(7c), independently represents a hydrogen atom, analkyl group or a cycloalkyl group.

Each of R_(x) and R_(y) independently represents an alkyl group, acycloalkyl group, an allyl group or a vinyl group.

Any two or more members out of R_(1c) to R_(5c), a pair of R_(6c) andR_(7c), and a pair of R_(x) and R_(y) may combine together to form ringstructures respectively. This ring structure may contain an oxygen atom,a sulfur atom, an ester bond or an amido bond. Examples of the groupformed by combining any two or more members out of R_(1c) to R_(5c), apair of R_(6c) and R_(7c), or a pair of R_(x) and R_(y) include abutylene group and a pentylene group.

Zc⁻ represents a non-nucleophilic anion, and examples thereof are thesame as those of the non-nucleophilic anion of Z⁻ in formula (ZI).

The alkyl group as R_(1c) to R_(7c) may be either linear or branched andis, for example, an alkyl group having a carbon number of 1 to 20,preferably a linear or branched alkyl group having a carbon number of 1to 12 (e.g., methyl, ethyl, linear or branched propyl, linear orbranched butyl, linear or branched pentyl). The cycloalkyl group is, forexample, a cycloalkyl group having a carbon number of 3 to 8 (e.g.,cyclopentyl, cyclohexyl).

The alkoxy group as R_(1c) to R_(5c) may be linear, branched or cyclicand is, for example, an alkoxy group having a carbon number of 1 to 10,preferably a linear or branched alkoxy group having a carbon number of 1to 5 (e.g., methoxy, ethoxy, linear or branched propoxy, linear orbranched butoxy, linear or branched pentoxy) or a cyclic alkoxy grouphaving a carbon number of 3 to 8 (e.g., cyclopentyloxy, cyclohexyloxy).

A compound where any one of R_(1c) to R_(5c) is a linear or branchedalkyl group, a cycloalkyl group or a linear, branched or cyclic alkoxygroup is preferred, and a compound where the sum of carbon numbers ofR_(1c) to R_(5c) is from 2 to 15 is more preferred. Thanks to such acompound, the solvent solubility is more enhanced and production ofparticles during storage can be suppressed.

Examples of the alkyl group and cycloalkyl group as R_(x) and R_(y) arethe same as those of the alkyl group and cycloalkyl group in R_(1c) toR_(7c). Among these, a 2-oxoalkyl group, a 2-oxocycloalkyl group and analkoxycarbonylmethyl group are preferred.

Examples of the 2-oxoalkyl group and 2-oxocycloalkyl group include agroup having >C═O at the 2-position of the alkyl group or cycloalkylgroup as R_(1c) to R_(7c).

Examples of the alkoxy group in the alkoxycarbonylmethyl group are thesame as those of the alkoxy group in R_(1c) to R_(5c).

Each of R_(x) and R_(y) is preferably an alkyl or cycloalkyl grouphaving a carbon number of 4 or more, more preferably 6 or more, stillmore preferably 8 or more.

In formulae (ZII) and (ZIII), each of R₂₀₄ to R₂₀₇ independentlyrepresents an aryl group, an alkyl group or a cycloalkyl group.

The aryl group of R₂₀₄ to R₂₀₇ is preferably a phenyl group or anaphthyl group, more preferably a phenyl group. The aryl group of R₂₀₄to R₂₀₇ may be an aryl group having a heterocyclic structure containingan oxygen atom, a nitrogen atom, a sulfur atom or the like. Examples ofthe aryl group having a heterocyclic structure include a pyrrole residue(a group formed by removing one hydrogen atom from a pyrrole), a furanresidue (a group formed by removing one hydrogen atom from a furan), athiophene residue (a group formed by removing one hydrogen atom from athiophene), an indole residue (a group formed by removing one hydrogenatom from an indole), a benzofuran residue (a group formed by removingone hydrogen atom from a benzofuran) and a benzothiophene residue (agroup formed by removing one hydrogen atom from a benzothiophene).

The alkyl group and cycloalkyl group in R₂₀₄ to R₂₀₇ are preferably alinear or branched alkyl group having a carbon number of 1 to 10 (e.g.,methyl, ethyl, propyl, butyl, pentyl) and a cycloalkyl group having acarbon number of 3 to 10 (e.g., cyclopentyl, cyclohexyl, norbornyl).

Each of the aryl group, alkyl group and cycloalkyl group of R₂₀₄ to R₂₀₇may have a substituent. Examples of the substituent which the arylgroup, alkyl group and cycloalkyl group of R₂₀₄ to R₂₀₇ may have includean alkyl group (for example, an alkyl group having a carbon number of 1to 15), a cycloalkyl group (for example, a cycloalkyl group having acarbon number of 3 to 15), an aryl group (for example, an aryl grouphaving a carbon number of 6 to 15), an alkoxy group (for example, analkoxy group having a carbon number of 1 to 15), a halogen atom, ahydroxyl group and a phenylthio group.

Z⁻ represents a non-nucleophilic anion, and examples thereof are thesame as those of the non-nucleophilic anion of Z⁻ in formula (ZI).

Other examples of the acid generator include compounds represented bythe following formulae (ZIV), (ZV) and (ZVI):

In formulae (ZIV) to (ZVI), each of Ar₃ and Ar₄ independently representsan aryl group.

Each of R₂₀₈, R₂₀₉ and R₂₁₀ independently represents an alkyl group, acycloalkyl group or an aryl group.

A represents an alkylene group, an alkenylene group or an arylene group.

Among the acid generators, more preferred are the compounds representedby formulae (ZI) to (ZIII).

The acid generator is preferably a compound that generates an acidhaving one sulfonic acid group or imide group, more preferably acompound that generates a monovalent perfluoroalkanesulfonic acid, acompound that generates a monovalent aromatic sulfonic acid substitutedby a fluorine atom or a fluorine atom-containing group, or a compoundthat generates a monovalent imide acid substituted by a fluorine atom ora fluorine atom-containing group, still more preferably a sulfonium saltof fluoro-substituted alkanesulfonic acid, fluorine-substitutedbenzenesulfonic acid, fluorine-substituted imide acid orfluorine-substituted methide acid. In particular, the acid generatedfrom the acid generator which can be used is preferably afluoro-substituted alkanesulfonic acid, fluoro-substitutedbenzenesulfonic acid or fluoro-substituted imide acid having a pKa of −1or less and in this case, the sensitivity can be enhanced.

Out of the acid generators, particularly preferred examples are setforth below.

It is also preferred that the positive resist composition for immersionexposure of the present invention contains, as the acid generator, acompound capable of generating an acid corresponding to the anion moietyin formula (I) upon irradiation with an actinic ray or radiation.

(wherein X⁺ represents an organic counter ion, and R represents ahydrogen atom or an organic group).

In formula (I), R represents a hydrogen atom or an organic group and ispreferably an organic group having a carbon number of 1 to 40, morepreferably an organic group having a carbon number of 3 to 20, and mostpreferably an organic group represented by the following formula (II).

The organic group of R is sufficient if it has one or more carbon atoms.The organic group is preferably an organic group where the atom bondedto the oxygen atom in the ester bond shown in formula (I) is a carbonatom, and examples thereof include an alkyl group, a cycloalkyl group,an aryl group, an aralkyl group and a group having a lactone structure.The organic group may contain a heteroatom such as oxygen atom andsulfur atom in the chain. Also, one of these groups may have another asa substituent, or the organic group may have a substituent such ashydroxyl group, acyl group, acyloxy group, oxy group (═O) or halogenatom.—(CH₂)_(n)-Rc-(Y)_(m)  (II)

In formula (II), Rc represents a monocyclic or polycyclic organic grouphaving a carbon number of 3 to 30 which may contain a cyclic ether,cyclic thioether, cyclic ketone, cyclic carbonate ester, lactone orlactam structure; Y represents a hydroxyl group, a halogen atom, a cyanogroup, a carboxyl group, a hydrocarbon group having a carbon number of 1to 10, a hydroxyalkyl group having a carbon number of 1 to 10, an alkoxygroup having a carbon number of 1 to 10, an acyl group having a carbonnumber of 1 to 10, an alkoxycarbonyl group having a carbon number of 2to 10, an acyloxy group having a carbon number of 2 to 10, analkoxyalkyl group having a carbon number of 2 to 10, or an alkyl halidegroup having a carbon number of 1 to 8; m=from 0 to 6; when a pluralityof Y's are present, each Y may be the same as or different from everyother Y; and n=from 0 to 10.

The total number of carbon atoms constituting the R group represented byformula (II) is preferably 40 or less.

It is preferred that n=from 0 to 3 and Rc is a monocyclic or polycyclicorganic group having a carbon number of 7 to 16.

The molecular weight of the compound represented by formula (I) isgenerally from 300 to 1,000, preferably from 400 to 800, more preferablyfrom 500 to 700.

Examples of the organic counter ion of X⁺ include sulfonium cation andiodonium cation.

The preferred embodiment of the compound represented by formula (I)includes a compound represented by formula (Z_(SC1)) or (Z_(IC1)).

In formula (Z_(SC1)), the definition and preferred range of R are thesame as those defined in formula (I).

Each of R₂₀₁, R₂₀₂ and R₂₀₃ independently represents an organic group.

The carbon number of the organic group as R₂₀₁, R₂₀₂ and R₂₀₃ isgenerally from 1 to 30, preferably from 1 to 20.

Two members out of R₂₀₁ to R₂₀₃ may combine to form a ring structure,and the ring may contain an oxygen atom, a sulfur atom, an ester bond,an amide bond or a carbonyl group. Examples of the group formed bycombining two members out of R₂₀₁ to R₂₀₃ include an alkylene group(e.g., butylene, pentylene).

Examples of the organic group as R₂₀₁, R₂₀₂ and R₂₀₃ includecorresponding groups in the compounds (Z_(SC1)-1), (Z_(SC1)-2) and(Z_(SC1)-3) which are described later.

The compound may be a compound having a plurality of structuresrepresented by formula (Z_(SC1)). For example, the compound may be acompound having a structure where at least one of R₂₀₁ to R₂₀₃ in thecompound represented by formula (Z_(SC1)) is bonded to at least one ofR₂₀₁ to R₂₀₃ in another compound represented by formula (Z_(SC1)).

The component (Z_(SC1)) is more preferably a compound (Z_(SC1)-1),(Z_(SC1)-2) or (Z_(SC1)-3) described below.

The compound (Z_(SC1)-1) is an arylsulfonium compound where at least oneof R₂₀₁ to R₂₀₃ in formula (Z_(SC1)) is an aryl group, that is, acompound having arylsulfonium as the cation.

The definition and preferred range of R are the same as those defined informula (I).

In the arylsulfonium compound, all of R₂₀₁ to R₂₀₃ may be an aryl groupor a part of R₂₀₁ to R₂₀₃ may be an aryl group with the remaining beingan alkyl group or a cycloalkyl group.

Examples of the arylsulfonium compound include a triarylsulfoniumcompound, a diarylalkylsulfonium compound, an aryldialkylsulfoniumcompound, a diarylcycloalkylsulfonium compound and anaryldicycloalkylsulfonium compound.

The aryl group in the arylsulfonium compound is preferably a phenylgroup or a naphthyl group, more preferably a phenyl group. The arylgroup may be an aryl group having a heterocyclic structure containing anoxygen atom, a nitrogen atom, a sulfur atom or the like. Examples of thearyl group having a heterocyclic structure include a pyrrole residue (agroup formed by removing one hydrogen atom from a pyrrole), a furanresidue (a group formed by removing one hydrogen atom from a furan), athiophene residue (a group formed by removing one hydrogen atom from athiophene), an indole residue (a group formed by removing one hydrogenatom from an indole), a benzofuran residue (a group formed by removingone hydrogen atom from a benzofuran) and a benzothiophene residue (agroup formed by removing one hydrogen atom from a benzothiophene). Inthe case where the arylsulfonium compound has two or more aryl groups,these two or more aryl groups may be the same or different.

The alkyl or cycloalkyl group which is present, if desired, in thearylsulfonium compound is preferably a linear or branched alkyl grouphaving a carbon number of 1 to 15 or a cycloalkyl group having a carbonnumber of 3 to 15, and examples thereof include a methyl group, an ethylgroup, a propyl group, an n-butyl group, a sec-butyl group, a tert-butylgroup, a cyclopropyl group, a cyclobutyl group and a cyclohexyl group.

Each of the aryl group, alkyl group and cycloalkyl group of R₂₀₁ to R₂₀₃may have, as the substituent, an alkyl group (for example, an alkylgroup having a carbon number of 1 to 15), a cycloalkyl group (forexample, a cycloalkyl group having a carbon number of 3 to 15), an arylgroup (for example, an aryl group having a carbon number of 6 to 14), analkoxy group (for example, an alkoxy group having a carbon number of 1to 15), a halogen atom, a hydroxyl group or a phenylthio group. Thesubstituent is preferably a linear or branched alkyl group having acarbon number of 1 to 12, a cycloalkyl group having a carbon number of 3to 12, or a linear, branched or cyclic alkoxy group having a carbonnumber of 1 to 12, more preferably an alkyl group having a carbon numberof 1 to 4, or an alkoxy group having a carbon number of 1 to 4. Thesubstituent may be substituted to any one of three members R₂₀₁ to R₂₀₃or may be substituted to all of these three members. In the case whereR₂₀₁ to R₂₀₃ are an aryl group, the substituent is preferablysubstituted at the p-position of the aryl group.

The compound (Z_(SC1)-2) is described below.

The definition and preferred range of R are the same as those defined informula (I).

The compound (Z_(SC1)-2) is a compound where each of R₂₀₁ to R₂₀₃ informula (Z_(SC1)) independently represents an aromatic ring-free organicgroup. The aromatic ring as used herein includes an aromatic ringcontaining a heteroatom.

The aromatic ring-free organic group as R₂₀₁ to R₂₀₃ has a carbon numberof generally from 1 to 30, preferably from 1 to 20.

Each of R₂₀₁ to R₂₀₃ independently represents preferably an alkyl group,a cycloalkyl group, an allyl group or a vinyl group, more preferably alinear or branched 2-oxoalkyl group, a 2-oxocycloalkyl group or analkoxycarbonylmethyl group, still more preferably a linear or branched2-oxoalkyl group.

The alkyl group and cycloalkyl group of R₂₀₁ to R₂₀₃ are preferably alinear or branched alkyl group having a carbon number of 1 to 10 (e.g.,methyl, ethyl, propyl, butyl, pentyl) and a cycloalkyl group having acarbon number of 3 to 10 (e.g., cyclopentyl, cyclohexyl, norbornyl). Thealkyl group is more preferably a 2-oxoalkyl group or analkoxycarbonylmethyl group. The cycloalkyl group is more preferably a2-oxocycloalkyl group.

The 2-oxoalkyl group may be either linear or branched and is preferablya group having >C═O at the 2-position of the above-described alkylgroup.

The 2-oxocycloalkyl group is preferably a group having >C═O at the2-position of the above-described cycloalkyl group.

The alkoxy group in the alkoxycarbonylmethyl group is preferably analkoxy group having a carbon number of 1 to 5 (e.g., methoxy, ethoxy,propoxy, butoxy, pentoxy).

Each of R₂₀₁ to R₂₀₃ may be further substituted by a halogen atom, analkoxy group (for example, an alkoxy group having a carbon number of 1to 5), a hydroxyl group, a cyano group or a nitro group.

The compound (Z_(SC1)-3) is a compound represented by the followingformula (Z_(SC1)-3), and this is a compound having a phenacylsulfoniumsalt structure.

In formula (Z_(SC1)-3), the definition and preferred range of R are thesame as those defined in formula (I).

Each of R_(1c) to R_(5c) independently represents a hydrogen atom, analkyl group, a cycloalkyl group, an alkoxy group or a halogen atom.

Each of R_(6c) and R_(7c) independently represents a hydrogen atom, analkyl group or a cycloalkyl group.

Each of R_(x) and R_(y) independently represents an alkyl group, acycloalkyl group, an allyl group or a vinyl group.

Any two or more members out of R_(1c) to R_(5c) a pair of R_(6c) andR_(7c), and a pair of R_(x) and R_(y) may combine together to form ringstructures respectively. This ring structure may contain an oxygen atom,a sulfur atom, an ester bond or an amido bond. Examples of the groupformed by combining any two or more members out of R_(1c) to R_(5c), apair of R_(6c) and R_(7c), or a pair of R_(x) and R_(y) include abutylene group and a pentylene group.

The alkyl group as R_(1c) to R_(7c) may be either linear or branched andis, for example, an alkyl group having a carbon number of 1 to 20,preferably a linear or branched alkyl group having a carbon number of 1to 12 (e.g., methyl, ethyl, linear or branched propyl, linear orbranched butyl, linear or branched pentyl). The cycloalkyl group is, forexample, a cycloalkyl group having a carbon number of 3 to 8 (e.g.,cyclopentyl, cyclohexyl).

The alkoxy group as R_(1c) to R_(5c) may be linear, branched or cyclicand is, for example, an alkoxy group having a carbon number of 1 to 10,preferably a linear or branched alkoxy group having a carbon number of 1to 5 (e.g., methoxy, ethoxy, linear or branched propoxy, linear orbranched butoxy, linear or branched pentoxy) or a cyclic alkoxy grouphaving a carbon number of 3 to 8 (e.g., cyclopentyloxy, cyclohexyloxy).

A compound where any one of R_(1c) to R_(5c) is a linear or branchedalkyl group, a cycloalkyl group or a linear, branched or cyclic alkoxygroup is preferred, and a compound where the sum of carbon numbers ofR_(1c) to R_(5c) is from 2 to 15 is more preferred. Thanks to such acompound, the solvent solubility is more enhanced and production ofparticles during storage can be suppressed.

Examples of the alkyl group and cycloalkyl group as R_(x) and R_(y) arethe same as those of the alkyl group and cycloalkyl group in R_(1c) toR_(7c). Among these, a 2-oxoalkyl group, a 2-oxocycloalkyl group and analkoxycarbonylmethyl group are preferred.

Examples of the 2-oxoalkyl group and 2-oxocycloalkyl group include agroup having >C═O at the 2-position of the alkyl group or cycloalkylgroup as R_(1c) to R_(7c).

Examples of the alkoxy group in the alkoxycarbonylmethyl group are thesame as those of the alkoxy group in R_(1c) to R_(5c).

Each of R_(x) and R_(y) is preferably an alkyl or cycloalkyl grouphaving a carbon number of 4 or more, more preferably 6 or more, stillmore preferably 8 or more.

In formula (Z_(IC1)), the definition and preferred range of R are thesame as those defined in formula (I).

Each of R₂₀₄ and R₂₀₅ independently represents an aryl group, an alkylgroup or a cycloalkyl group.

The aryl group of R₂₀₄ and R₂₀₅ is preferably a phenyl group or anaphthyl group, more preferably a phenyl group. The aryl group of R₂₀₄and R₂₀₅ may be an aryl group having a heterocyclic structure containingan oxygen atom, a nitrogen atom, a sulfur atom or the like. Examples ofthe aryl group having a heterocyclic structure include a pyrrole residue(a group formed by removing one hydrogen atom from a pyrrole), a furanresidue (a group formed by removing one hydrogen atom from a furan), athiophene residue (a group formed by removing one hydrogen atom from athiophene), an indole residue (a group formed by removing one hydrogenatom from an indole), a benzofuran residue (a group formed by removingone hydrogen atom from a benzofuran) and a benzothiophene residue (agroup formed by removing one hydrogen atom from a benzothiophene).

The alkyl group and cycloalkyl group in R₂₀₄ and R₂₀₅ are preferably alinear or branched alkyl group having a carbon number of 1 to 10 (e.g.,methyl, ethyl, propyl, butyl, pentyl) and a cycloalkyl group having acarbon number of 3 to 10 (e.g., cyclopentyl, cyclohexyl, norbornyl).

Each of the aryl group, alkyl group and cycloalkyl group of R₂₀₄ andR₂₀₅ may have a substituent. Examples of the substituent which the arylgroup, alkyl group and cycloalkyl group of R₂₀₄ and R₂₀₅ may haveinclude an alkyl group (for example, an alkyl group having a carbonnumber of 1 to 15), a cycloalkyl group (for example, a cycloalkyl grouphaving a carbon number of 3 to 15), an aryl group (for example, an arylgroup having a carbon number of 6 to 15), an alkoxy group (for example,an alkoxy group having a carbon number of 1 to 15), a halogen atom, ahydroxyl group and a phenylthio group.

Specific examples of the compound represented by formula (I) include,but are not limited to, the compounds set forth below.

The compound represented by formula (I) can be synthesized by a knownmethod, for example, can be synthesized in accordance with the methoddescribed in JPA-2007-161707.

As for the compound represented by formula (I), one kind may be used, ortwo or more kinds may be used in combination.

One kind of an acid generator may be used alone, or two or more kinds ofacid generators may be used in combination.

The content of the acid generator in the positive resist composition forimmersion exposure is preferably from 0.1 to 20 mass %, more preferablyfrom 0.5 to 10 mass %, still more preferably from 1 to 7 mass %, basedon the entire solid content of the resist composition.

[3] (C) Resin Having at Least Either a Fluorine Atom or a Silicon Atom

The positive resist composition for immersion exposure of the presentinvention contains (C) a resin having at least either a fluorine atom ora silicon atom (hydrophobic resin (C)).

When the composition contains the resin (C), the resin (C) having atleast either a fluorine atom or a silicon atom is unevenly distributedto the surface layer of the resist film and in the case of using wateras the immersion medium, the resist film formed can be enhanced in thereceding contact angle on the resist film surface for water as well asin the followability of the immersion liquid.

The receding contact angle of the resist film is preferably from 60 to90°, more preferably 70° or more. The amount added of the resin may beappropriately adjusted so that the resist film can have a recedingcontact angle in the above-described range, but the resin is preferablyused in an amount of 0.01 to 10 mass %, more preferably from 0.05 to 8mass %, still more preferably from 0.1 to 5 mass %, based on the entiresolid content of the resist composition.

The resin (C) having at least either a fluorine atom or a silicon atomis, as described above, unevenly distributed to the interface but unlikea surfactant, need not have necessarily a hydrophilic group in themolecule and may not contribute to uniform mixing of polar/nonpolarsubstances.

The receding contact angle is a contact angle measured when a contactline recedes on the liquid droplet-substrate interface, and is generallyknown to be useful in simulating the mobility of a liquid droplet in thedynamic state. In a simple manner, the receding contact angle can bedefined as a contact angle at the time of the liquid droplet interfacereceding when a liquid droplet ejected from a needle tip is landed on asubstrate and then the liquid droplet is again sucked into the needle.In general, the receding contact angle can be measured by a contactangle measuring method called an expansion/contraction method.

In the immersion exposure step, the immersion liquid needs to move on awafer following the movement of an exposure head that is scanning thewafer at a high speed and forming an exposure pattern. Therefore, thecontact angle of the immersion liquid with the resist film in a dynamicstate is important and the resist is required to have a performance ofallowing a liquid droplet to follow the high-speed scanning of anexposure head with no remaining of the liquid droplet.

The fluorine atom or silicon atom in the resin (C) having at leasteither a fluorine atom or a silicon atom may be present in the mainchain of the resin or may be substituted to the side chain.

The resin (C) having at least either a fluorine atom or a silicon atomis preferably a resin having a fluorine atom-containing alkyl group, afluorine atom-containing cycloalkyl group or a fluorine atom-containingaryl group, as a fluorine atom-containing partial structure.

The fluorine atom-containing alkyl group (preferably having a carbonnumber of 1 to 10, more preferably from 1 to 4) is a linear or branchedalkyl group with at least one hydrogen atom being substituted by afluorine atom and may further have other substituents.

The fluorine atom-containing cycloalkyl group is a monocyclic orpolycyclic cycloalkyl group with at least one hydrogen atom beingsubstituted by a fluorine atom and may further have other substituents.

The fluorine atom-containing aryl group is an aryl group (e.g., phenyl,naphthyl) with at least one hydrogen atom being substituted by afluorine atom and may further have other substituents.

Preferred examples of the fluorine atom-containing alkyl group, fluorineatom-containing cycloalkyl group and fluorine atom-containing aryl groupinclude the groups represented by the following formulae (F2) to (F4),but the present invention is not limited thereto.

In formulae (F2) to (F4), each of R₅₇ to R₆₈ independently represents ahydrogen atom, a fluorine atom, an alkyl group, a cycloalkyl group or anaryl group, provided that at least one of R₅₇ to R₆₁, at least one ofR₆₂ to R₆₄ and at least one of R₆₅ to R_(6g) are a fluorine atom or analkyl group (preferably having a carbon number of 1 to 4), cycloalkylgroup or aryl group with at least one hydrogen atom being substituted bya fluorine atom. R₆₂ and R₆₃ may combine with each other to form a ring.

It is preferred that all of R₅₇ to R₆₁ and R₆₅ to R₆₇ are a fluorineatom. Each of R₆₂, R₆₃ and R₆₈ is preferably an alkyl group (preferablyhaving a carbon number of 1 to 4) with at least one hydrogen atom beingsubstituted by a fluorine atom, more preferably a perfluoroalkyl grouphaving a carbon number of 1 to 4. R₆₂ and R₆₃ may combine with eachother to form a ring.

Specific examples of the group represented by formula (F2) includep-fluorophenyl group, pentafluorophenyl group and3,5-di(trifluoromethyl)phenyl group.

Specific examples of the group represented by formula (F3) includetrifluoromethyl group, pentafluoropropyl group, pentafluoroethyl group,heptafluorobutyl group, hexafluoroisopropyl group, heptafluoroisopropylgroup, hexafluoro(2-methyl)isopropyl group, nonafluorobutyl group,octafluoroisobutyl group, nonafluorohexyl group, nonafluoro-tert-butylgroup, perfluoroisopentyl group, perfluorooctyl group,perfluoro(trimethyl)hexyl group, 2,2,3,3-tetrafluorocyclobutyl group andperfluorocyclohexyl group. Among these, hexafluoroisopropyl group,heptafluoroisopropyl group, hexafluoro(2-methyl)isopropyl group,octafluoroisobutyl group, nonafluoro-tert-butyl group andperfluoroisopentyl group are preferred, and hexafluoroisopropyl groupand heptafluoroisopropyl group are more preferred.

Specific examples of the group represented by formula (F4) include—C(CF₃)₂OH, —C(C₂F₅)₂OH, —C(CF₃)(CH₃)OH and —CH(CF₃)OH, with —C(CF₃)₂OHbeing preferred.

Specific examples of the repeating unit having a fluorine atom are setforth below, but the present invention is not limited thereto.

In specific examples, X₁ represents a hydrogen atom, —CH₃, —F or —CF₃.

X₂ represents —F or —CF₃.

The resin (C) having at least either a fluorine atom or a silicon atommay contain a silicon atom and is preferably a resin having analkylsilyl structure (preferably a trialkylsilyl group) or a cyclicsiloxane structure, as a silicon atom-containing partial structure.

Specific examples of the alkylsilyl structure and cyclic siloxanestructure include the groups represented by the following formulae(CS-1) to (CS-3):

In formulae (CS-1) to (CS-3), each of R₁₂ to R₂₆ independentlyrepresents a linear or branched alkyl group (preferably having a carbonnumber of 1 to 20) or a cycloalkyl group (preferably having a carbonnumber of 3 to 20).

Each of L₃ to L₅ represents a single bond or a divalent linking group.The divalent linking group is a single group or a combination of two ormore groups, selected from the group consisting of an alkylene group, aphenylene group, an ether group, a thioether group, a carbonyl group, anester group, an amide group, a urethane group and a urea group.

n represents an integer of 1 to 5. n is preferably an integer of 2 to 4.

Specific examples of the repeating unit having a group represented byformula (CS-1) to (CS-3) are set forth below, but the present inventionis not limited thereto. In specific examples, X₁ represents a hydrogenatom, —CH₃, —F or —CF₃.

The resin (C) more preferably contains at least one kind of an acrylateor methacrylate-derived repeating unit having a group represented by anyone of formulae (F2) to (F4) and (CS-1) to (CS-3).

Furthermore, the resin (C) having at least either a fluorine atom or asilicon atom may contain at least one group selected from the groupconsisting of the following (x) to (z):

(x) an alkali-soluble group,

(y) a group capable of decomposing by the action of an alkali developerto increase the solubility in an alkali developer, and

(z) a group capable of decomposing by the action of an acid.

Examples of the (x) alkali-soluble group include a phenolic hydroxylgroup, a carboxylic acid group, a fluorinated alcohol group, a sulfonicacid group, a sulfonamide group, a sulfonylimide group, an(alkylsulfonyl)(alkylcarbonyl)methylene group, an(alkylsulfonyl)(alkylcarbonyl)imide group, a bis(alkylcarbonyl)methylenegroup, a bis(alkylcarbonyl)imide group, a bis(alkylsulfonyl)methylenegroup, a bis(alkylsulfonyl)imide group, a tris(alkylcarbonyl)methylenegroup and a tris(alkylsulfonyl)methylene group.

Preferred alkali-soluble groups include a fluorinated alcohol group(preferably hexafluoroisopropanol), a sulfonimide group and abis(carbonyl)methylene group.

The repeating unit having (x) an alkali-soluble group includes arepeating unit where an alkali-soluble group is directly bonded to theresin main chain, such as repeating unit by an acrylic acid or amethacrylic acid, and a repeating unit where an alkali-soluble group isbonded to the resin main chain through a linking group. Furthermore, analkali-soluble group may also be introduced into the polymer chainterminal by using an alkali-soluble group-containing polymerizationinitiator or chain transfer agent at the polymerization. All of theserepeating units are preferred.

The content of the repeating unit having (x) an alkali-soluble group ispreferably from 1 to 50 mol %, more preferably from 3 to 35 mol %, stillmore preferably from 5 to 20 mol %, based on all repeating units in thepolymer.

Specific examples of the repeating unit having (x) an alkali-solublegroup are set forth below, but the present invention is not limitedthereto. In the formulae, Rx represents H, CH₃, CH₂OH or CF₃.

Examples of the (y) group capable of decomposing by the action of analkali developer to increase the solubility in an alkali developerinclude a lactone structure-containing group, an acid anhydride groupand an acid imide group, with a lactone structure-containing group beingpreferred.

As for the repeating unit having (y) a group capable of decomposing bythe action of an alkali developer to increase the solubility in analkali developer, both a repeating unit where (y) a group capable ofdecomposing by the action of an alkali developer to increase thesolubility in an alkali developer is bonded to the main chain of resin,such as repeating unit by an acrylic acid ester or a methacrylic acidester, and a repeating unit where (y) a group capable of increasing thesolubility in an alkali developer is introduced into the polymer chainterminal by using a polymerization initiator or chain transfer agentcontaining this group at the polymerization are preferred.

The content of the repeating unit having (y) a group capable ofincreasing the solubility in an alkali developer is preferably from 1 to40 mol %, more preferably from 3 to 30 mol %, still more preferably from5 to 15 mol %, based on all repeating units in the polymer.

Specific examples of the repeating unit having (y) a group capable ofincreasing the solubility in an alkali developer are the same as thoseof the repeating unit having a lactone structure described for the resinas the component (B).

Examples of the repeating unit having (z) a group capable of decomposingby the action of an acid, contained in the resin (C) having at leasteither a fluorine atom or a silicon atom, are the same as those of therepeating unit having an acid-decomposable group described for the resinas the component (B). In the resin (C) having at least either a fluorineatom or a silicon atom, the content of the repeating unit having (z) agroup capable of decomposing by the action of an acid is preferably from1 to 80 mol %, more preferably from 10 to 80 mol %, still morepreferably from 20 to 60 mol %, based on all repeating units in thepolymer.

The resin (C) having at least either a fluorine atom or a silicon atommay further contain a repeating unit represented by the followingformula (III):

In formula (III), R_(c31) represents a hydrogen atom, an alkyl group, analkyl group which may be substituted by fluorine, a cyano group or—CH₂—O-Rac₂, wherein Rac₂ represents a hydrogen atom, an alkyl group oran acyl group. R_(c31) is preferably a hydrogen atom, a methyl group, ahydroxymethyl group or a trifluoromethyl group, more preferably ahydrogen atom or a methyl group.

R_(c32) represents a group having an alkyl group, a cycloalkyl group, analkenyl group or a cycloalkenyl group. Such a group may be substitutedby a fluorine atom or a silicon atom.

L_(c3) represents a single bond or a divalent linking group.

In formula (III), the alkyl group of R_(c32) is preferably a linear orbranched alkyl group having a carbon number of 3 to 20.

The cycloalkyl group is preferably a cycloalkyl group having a carbonnumber of 3 to 20.

The alkenyl group is preferably an alkenyl group having a carbon numberof 3 to 20.

The cycloalkenyl group is preferably a cycloalkenyl group having acarbon number of 3 to 20.

R_(c32) is preferably an unsubstituted alkyl group or an alkyl groupsubstituted by a fluorine atom.

The divalent linking group of L_(c3) is preferably an ester group, analkylene group (preferably having a carbon number of 1 to 5), an oxygroup, a phenylene group or an ester bond (a group represented by—COO—).

It is also preferred that the resin (C) having at least either afluorine atom or a silicon atom further contains a repeating unitrepresented by the following formula (CII-AB).

In formula (CII-AB), each of R_(c11)′ and R_(c12)′ independentlyrepresents a hydrogen atom, a cyano group, a halogen atom or an alkylgroup.

Zc′ represents an atomic group for forming an alicyclic structurecontaining the two bonded carbon atoms (C—C).

Specific examples of the repeating units represented by formulae (VI)and (CII-AB) are set forth below, but the present invention is notlimited thereto. In the formulae, Ra represents H, CH₃, CH₂OH, CF₃ orCN.

In the case where the resin (C) having at least either a fluorine atomor a silicon atom contains a fluorine atom, the fluorine atom content ispreferably from 5 to 80 mass %, more preferably from 10 to 80 mass %,based on the molecular weight of the resin (C) having at least either afluorine atom or a silicon atom. Also, the fluorine atom-containingrepeating unit preferably occupies from 10 to 100 mass %, morepreferably from 30 to 100 mass %, in the resin (C) having at leasteither a fluorine atom or a silicon atom.

In the case where the resin (C) having at least either a fluorine atomor a silicon atom contains a silicon atom, the silicon atom content ispreferably from 2 to 50 mass %, more preferably from 2 to 30 mass %,based on the molecular weight of the resin (C) having at least either afluorine atom or a silicon atom. Also, the silicon atom-containingrepeating unit preferably occupies from 10 to 100 mass %, morepreferably from 20 to 100 mass %, in the resin (C) having at leasteither a fluorine atom or a silicon atom.

The standard polystyrene-reduced weight average molecular of the resin(C) having at least either a fluorine atom or a silicon atom ispreferably from 1,000 to 100,000, more preferably from 1,000 to 50,000,still more preferably from 2,000 to 15,000.

Similarly to the resin as the component (B), in the resin (C) having atleast either a fluorine atom or a silicon atom, it is of coursepreferred that the amount of impurities such as metal is small, andalso, the content of the residual monomers or oligomer components ispreferably from 0 to 10 mass %, more preferably from 0 to 5 mass %,still more preferably from 0 to 1 mass %. By satisfying theseconditions, a resist free of extraneous substances in the liquid orchange with aging in the sensitivity and the like can be obtained.Furthermore, in view of resolution, resist profile, side wall of resistpattern, roughness and the like, the molecular weight distribution(Mw/Mn, also called polydispersity) is preferably from 1 to 5, morepreferably from 1 to 3, still more preferably from 1 to 2.

As for the resin (C) having at least either a fluorine atom or a siliconatom, various commercially available products may be used or the resinmay be synthesized by an ordinary method (for example, radicalpolymerization)). Examples of the synthesis method in general include abatch polymerization method of dissolving monomer species and aninitiator in a solvent and heating the solution, thereby effecting thepolymerization, and a dropping polymerization method of adding dropwisea solution containing monomer species and an initiator to a heatedsolvent over 1 to 10 hours. A dropping polymerization method ispreferred. Examples of the reaction solvent include tetrahydrofuran,1,4-dioxane, ethers such as diisopropyl ether, ketones such as methylethyl ketone and methyl isobutyl ketone, an ester solvent such as ethylacetate, an amide solvent such as dimethylformamide anddimethylacetamide, and a solvent capable of dissolving the compositionof the present invention, which is described later, such as propyleneglycol monomethyl ether acetate, propylene glycol monomethyl ether andcyclohexanone. The polymerization is more preferably performed using thesame solvent as the solvent used in the positive resist composition forimmersion exposure of the present invention. By the use of the samesolvent, production of particles during storage can be suppressed.

The polymerization reaction is preferably performed in an inert gasatmosphere such as nitrogen or argon. As for the polymerizationinitiator, the polymerization is initiated using a commerciallyavailable radical initiator (e.g., azo-based initiator, peroxide). Theradical initiator is preferably an azo-based initiator, and an azo-basedinitiator having an ester group, a cyano group or a carboxyl group ispreferred. Preferred examples of the initiator includeazobisisobutyronitrile, azobisdimethylvaleronitrile and dimethyl2,2′-azobis(2-methylpropionate). The reaction concentration is from 5 to50 mass %, preferably from 30 to 50 mass %, and the reaction temperatureis usually from 10 to 150° C., preferably from 30 to 120° C., morepreferably from 60 to 100° C.

After the completion of reaction, the reaction solution is allowed tocool to room temperature and purified. The purification may be performedby a normal method, for example, a liquid-liquid extraction method ofapplying water washing or combining an appropriate solvent to removeresidual monomers or oligomer components; a purification method in asolution sate, such as ultrafiltration of removing by extraction onlythose having a molecular weight not more than a specific value; areprecipitation method of adding dropwise the resin solution in a poorsolvent to solidify the resin in the poor solvent and thereby removeresidual monomers and the like; and a purification method in a solidstate, such as a method of subjecting a resin slurry separated byfiltration to washing with a poor solvent. For example, the resin isprecipitated as a solid by contacting the reaction solution with asolvent in which the resin is sparingly soluble or insoluble (poorsolvent) and which is in a volume amount of 10 times or less, preferablyfrom 10 to 5 times, the reaction solution.

The solvent used at the operation of precipitation or reprecipitationfrom the polymer solution (precipitation or reprecipitation solvent) maybe sufficient if it is a poor solvent to the polymer, and the solventmay be appropriately selected, for example, from a hydrocarbon, ahalogenated hydrocarbon, a nitro compound, an ether, a ketone, an ester,a carbonate, an alcohol, a carboxylic acid, water, and a mixed solventcontaining such a solvent, according to the kind of the polymer. Amongthese solvents, a solvent containing at least an alcohol (particularly,methanol or the like) or water is preferred as the precipitation orreprecipitation solvent.

The amount of the precipitation or reprecipitation solvent used may beappropriately selected by taking into consideration the efficiency,yield and the like, but in general, the amount used is from 100 to10,000 parts by mass, preferably from 200 to 2,000 parts by mass, morepreferably from 300 to 1,000 parts by mass, per 100 parts by mass of thepolymer solution.

The temperature at the precipitation or reprecipitation may beappropriately selected by taking into consideration the efficiency oroperability but is usually on the order of 0 to 50° C., preferably inthe vicinity of room temperature (for example, approximately from 20 to35° C.). The precipitation or reprecipitation operation may be performedusing a commonly employed mixing vessel such as stirring tank, by aknown method such as batch system and continuous system.

The precipitated or reprecipitated polymer is usually subjected tocommonly employed solid-liquid separation such as filtration andcentrifugation, then dried and used. The filtration is performed using asolvent-resistant filter element preferably under pressure. The dryingis performed under atmospheric pressure or reduced pressure (preferablyunder reduced pressure) at a temperature of approximately from 30 to100° C., preferably on the order of 30 to 50° C.

Incidentally, after the resin is once precipitated and separated, theresin may be again dissolved in a solvent and then put into contact witha solvent in which the resin is sparingly soluble or insoluble. That is,there may be used a method comprising, after the completion of radicalpolymerization reaction, bringing the polymer into contact with asolvent in which the polymer is sparingly soluble or insoluble, toprecipitate a resin (step a), separating the resin from the solution(step b), anew dissolving the resin in a solvent to prepare a resinsolution A (step c), bringing the resin solution A into contact with asolvent in which the resin is sparingly soluble or insoluble and whichis in a volume amount of less than 10 times (preferably 5 times or less)the resin solution A, to precipitate a resin solid (step d), andseparating the precipitated resin (step e).

Specific examples of the resin (C) having at least either a fluorineatom or a silicon atom are set forth below. Also, the molar ratio ofrepeating units (corresponding to repeating units from the left), weightaverage molecular weight and polydispersity of each resin are shown inTable 1 below.

TABLE 1 Resin Composition Mw Mw/Mn HR-1  50/50 4900 1.4 HR-2  50/50 51001.6 HR-3  50/50 4800 1.5 HR-4  50/50 5300 1.6 HR-5  50/50 4500 1.4 HR-6 100 5500 1.6 HR-7  50/50 5800 1.9 HR-8  50/50 4200 1.3 HR-9  50/50 55001.8 HR-10 40/60 7500 1.6 HR-11 70/30 6600 1.8 HR-12 40/60 3900 1.3 HR-1350/50 9500 1.8 HR-14 50/50 5300 1.6 HR-15 100 6200 1.2 HR-16 100 56001.6 HR-17 100 4400 1.3 HR-18 50/50 4300 1.3 HR-19 50/50 6500 1.6 HR-2030/70 6500 1.5 HR-21 50/50 6000 1.6 HR-22 50/50 3000 1.2 HR-23 50/505000 1.5 HR-24 50/50 4500 1.4 HR-25 30/70 5000 1.4 HR-26 50/50 5500 1.6HR-27 50/50 3500 1.3 HR-28 50/50 6200 1.4 HR-29 50/50 6500 1.6 HR-3050/50 6500 1.6 HR-31 50/50 4500 1.4 HR-32 30/70 5000 1.6 HR-33 30/30/406500 1.8 HR-34 50/50 4000 1.3 HR-35 50/50 6500 1.7 HR-36 50/50 6000 1.5HR-37 50/50 5000 1.6 HR-38 50/50 4000 1.4 HR-39 20/80 6000 1.4 HR-4050/50 7000 1.4 HR-41 50/50 6500 1.6 HR-42 50/50 5200 1.6 HR-43 50/506000 1.4 HR-44 70/30 5500 1.6 HR-45 50/20/30 4200 1.4 HR-46 30/70 75001.6 HR-47 40/58/2 4300 1.4 HR-48 50/50 6800 1.6 HR-49 100 6500 1.5 HR-5050/50 6600 1.6 HR-51 30/20/50 6800 1.7 HR-52 95/5 5900 1.6 HR-5340/30/30 4500 1.3 HR-54 50/30/20 6500 1.8 HR-55 30/40/30 7000 1.5 HR-5660/40 5500 1.7 HR-57 40/40/20 4000 1.3 HR-58 60/40 3800 1.4 HR-59 80/207400 1.6 HR-60 40/40/15/5 4800 1.5 HR-61 60/40 5600 1.5 HR-62 50/50 59002.1 HR-63 80/20 7000 1.7 HR-64 100 5500 1.8 HR-65 50/50 9500 1.9[4] (D) Solvent

The positive resist composition for immersion exposure of the presentinvention contains (D) a mixed solvent containing at least one kind of asolvent selected from the group consisting of solvents represented byany one of the following formulae (S1) to (S3). Thanks to this mixedsolvent, the receding contact angle of the resist film with theimmersion liquid can be made large.

In the mixed solvent (D), from the standpoint of preventing adevelopment defect, the amount in total (total amount) of the solvent(s)represented by any one of formulae (S1) to (S3) is from 3 to 20 mass %,preferably from 3 to 10 mass %, based on all solvents.

In formulae (S1) to (S3), each of R₁ to R₇ independently represents analkyl group, a cycloalkyl group or an aryl group, and R₁ and R₂, R₃ andR₄, or R₆ and R₇ may combine with each other to form a ring.

In formulae (S1) to (S3), R₁ to R₇ are preferably an alkyl group, and itis more preferred that R₁ and R₂, R₃ and R₄, or R₆ and R₇ are combinedtogether to form a ring.

The solvent represented by any one of formulae (S1) to (S3) ispreferably a solvent having a boiling point (at 1 atm) of 150 to 250°C., more preferably from 180 to 250° C. Among the solvents representedby any one of formulae (S1) to (S3), the solvents represented by formula(S1) or (S2) are more preferred, and the solvents represented by formula(S1) are most preferred.

As the solvents represented by any one of formulae (S1) to (S3), forexample, a solvent having a lactone structure, such as γ-butyrolactone,a solvent having an alkylene carbonate structure, such as ethylenecarbonate, propylene carbonate and butylene carbonate, andN-methylpyrrolidone are preferred, a solvent having a lactone structureand a solvent having an alkylene carbonate structure are more preferred,γ-butyrolactone and propylene carbonate are still more preferred, andpropylene carbonate is most preferred.

The solvent other than the solvents represented by any one of formulae(S1) to (S3), which can be contained in the solvent (D) for use in thepresent invention, is not particularly limited but includes, forexample, a hydroxyl group-containing solvent and a hydroxyl group-freesolvent described below.

Examples of the hydroxyl group-containing solvent include ethyleneglycol, ethylene glycol monomethyl ether, ethylene glycol monoethylether, propylene glycol, propylene glycol monomethyl ether (PGME, alsoknown as 1-methoxy-2-propanol), propylene glycol monoethyl ether andethyl lactate. Among these, propylene glycol monomethyl ether and ethyllactate are preferred.

Examples of the hydroxy group-free solvent include propylene glycolmonomethyl ether acetate (PGMEA, also known as1-methoxy-2-acetoxypropane), ethyl ethoxypropionate, 2-heptanone,cyclohexanone, butyl acetate, N,N-dimethylacetamide and dimethylsulfoxide. Among these, propylene glycol monomethyl ether acetate, ethylethoxypropionate, 2-heptanone, cyclohexanone and butyl acetate arepreferred, and propylene glycol monomethyl ether acetate, ethylethoxypropionate and 2-heptanone are most preferred.

A mixed solvent containing the hydroxy group-free solvent in aproportion of 50 mass % or more is particularly preferred in view ofcoating uniformity.

The solvent (D) preferably contains propylene glycol monomethyl etheracetate.

The solvent (D) is more preferably a mixed solvent containing a hydroxylgroup-containing solvent, a hydroxyl group-free solvent and at least onesolvent selected from the group consisting of solvents represented byany one of formulae (S1) to (S3), still more preferably a mixed solventcontaining an alkylene glycol monoalkyl ether acetate, an alkyleneglycol monoalkyl ether and at least one solvent selected from the groupconsisting of solvents represented by any one of formulae (S1) to (S3).

[5] Basic Compound:

The positive resist composition for immersion exposure of the presentinvention preferably contains a basic compound for reducing the changeof performance with aging from exposure to heating.

Preferred examples of the basic compound include compounds having astructure represented by any one of the following formulae (A) to (E):

In formulae (A) and (E), each of R²⁰⁰, R₂₀₁ and R²⁰², which may be thesame or different, represents a hydrogen atom, an alkyl group(preferably having a carbon number of 1 to 20), a cycloalkyl group(preferably having a carbon number of 3 to 20) or an aryl group (havinga carbon number of 6 to 20), and R²⁰¹ and R²⁰² may combine with eachother to form a ring. Each of R²⁰³, R²⁰⁴, R²⁰⁵ and R²⁰⁶, which may bethe same or different, represents an alkyl group having a carbon numberof 1 to 20.

As for the alkyl group, the alkyl group having a substituent ispreferably an aminoalkyl group having a carbon number of 1 to 20, ahydroxyalkyl group having a carbon number of 1 to 20, or a cyanoalkylgroup having a carbon number of 1 to 20.

The alkyl group in these formulae (A) and (E) is more preferablyunsubstituted.

Preferred examples of the compound include guanidine, aminopyrrolidine,pyrazole, pyrazoline, piperazine, aminomorpholine, aminoalkylmorpholineand piperidine. More preferred examples of the compound include acompound having an imidazole structure, a diazabicyclo structure, anonium hydroxide structure, an onium carboxylate structure, atrialkylamine structure, an aniline structure or a pyridine structure;an alkylamine derivative having a hydroxyl group and/or an ether bond;and an aniline derivative having a hydroxyl group and/or an ether bond.

Examples of the compound having an imidazole structure includeimidazole, 2,4,5-triphenylimidazole, benzimidazole and2-phenylbenzimidazole. Examples of the compound having a diazabicyclostructure include 1,4-diazabicyclo[2,2,2]octane,1,5-diazabicyclo[4,3,0]non-5-ene and 1,8-diazabicyclo[5,4,0]undec-7-ene.Examples of the compound having an onium hydroxide structure includetetrabutylammonium hydroxide, triarylsulfonium hydroxide,phenacylsulfonium hydroxide and sulfonium hydroxide having a 2-oxoalkylgroup, specifically, triphenylsulfonium hydroxide,tris(tert-butylphenyl)sulfonium hydroxide, bis(tert-butylphenyl)iodoniumhydroxide, phenacylthiophenium hydroxide and 2-oxopropylthiopheniumhydroxide. Examples of the compound having an onium carboxylatestructure include a compound where the anion moiety of the compoundhaving an onium hydroxide structure becomes a carboxylate, such asacetate, adamantane-1-carboxylate and perfluoroalkyl carboxylate.Examples of the compound having a trialkylamine structure includetri(n-butyl)amine and tri(n-octyl)amine. Examples of the anilinecompound include 2,6-diisopropylaniline, N,N-dimethylaniline,N,N-dibutylaniline and N,N-dihexylaniline. Examples of the alkylaminederivative having a hydroxyl group and/or an ether bond includeethanolamine, diethanolamine, triethanolamine, N-phenyldiethanolamineand tris(methoxyethoxyethyl)amine. Examples of the aniline derivativehaving a hydroxyl group and/or an ether bond includeN,N-bis(hydroxyethyl)aniline.

Other preferred basic compounds include a phenoxy group-containing aminecompound, a phenoxy group-containing ammonium salt compound, a sulfonicacid ester group-containing amine compound and a sulfonic acid estergroup-containing ammonium salt compound.

As for the amine compound, a primary, secondary or tertiary aminecompound can be used, and an amine compound where at least one alkylgroup is bonded to the nitrogen atom is preferred. The amine compound ismore preferably a tertiary amine compound. In the amine compound, aslong as at least one alkyl group (preferably having a carbon number of 1to 20) is bonded to the nitrogen atom, a cycloalkyl group (preferablyhaving a carbon number of 3 to 20) or an aryl group (preferably having acarbon number of 6 to 12) may be bonded to the nitrogen atom, inaddition to the alkyl group. The amine compound preferably has an oxygenatom in the alkyl chain to form an oxyalkylene group. The number ofoxyalkylene groups within the molecule is 1 or more, preferably from 3to 9, more preferably from 4 to 6. Among oxyalkylene groups, anoxyethylene group (—CH₂CH₂O—) and an oxypropylene group (—CH(CH₃)CH₂O—or —CH₂CH₂CH₂O—) are preferred, and an oxyethylene group is morepreferred.

As for the ammonium salt compound, a primary, secondary, tertiary orquaternary ammonium salt compound can be used, and an ammonium saltcompound where at least one alkyl group is bonded to the nitrogen atomis preferred. In the ammonium salt compound, as long as at least onealkyl group (preferably having a carbon number of 1 to 20) is bonded tothe nitrogen atom, a cycloalkyl group (preferably having a carbon numberof 3 to 20) or an aryl group (preferably having a carbon number of 6 to12) may be bonded to the nitrogen atom, in addition to the alkyl group.The ammonium salt compound preferably has an oxygen atom in the alkylchain to form an oxyalkylene group. The number of oxyalkylene groupswithin the molecule is 1 or more, preferably from 3 to 9, morepreferably from 4 to 6. Among oxyalkylene groups, an oxyethylene group(—CH₂CH₂O—) and an oxypropylene group (—CH(CH₃)CH₂O— or —CH₂CH₂CH₂O—)are preferred, and an oxyethylene group is more preferred. Examples ofthe anion of the ammonium salt compound include a halogen atom, asulfonate, a borate and a phosphate, with a halogen atom and a sulfonatebeing preferred. The halogen atom is preferably chloride, bromide oriodide, and the sulfonate is preferably an organic sulfonate having acarbon number of 1 to 20. The organic sulfonate includes analkylsulfonate having a carbon number of 1 to 20 and an arylsulfonate.The alkyl group of the alkylsulfonate may have a substituent, andexamples of the substituent include fluorine, chlorine, bromine, analkoxy group, an acyl group and an aryl group. Specific examples of thealkylsulfonate include methanesulfonate, ethanesulfonate,butanesulfonate, hexanesulfonate, octanesulfonate, benzylsulfonate,trifluoromethanesulfonate, pentafluoroethanesulfonate andnonafluorobutanesulfonate. The aryl group of the arylsulfonate includesa benzene ring, a naphthalene ring and an anthracene ring. The benzenering, naphthalene ring and anthracene ring each may have a substituent,and the substituent is preferably a linear or branched alkyl grouphaving a carbon number of 1 to 6, or a cycloalkyl group having a carbonnumber of 3 to 6. Specific examples of the linear or branched alkylgroup and cycloalkyl group include methyl, ethyl, n-propyl, isopropyl,n-butyl, i-butyl, tert-butyl, n-hexyl and cyclohexyl. Other examples ofthe substituent include an alkoxy group having a carbon number of 1 to6, a halogen atom, cyano, nitro, an acyl group and an acyloxy group.

The phenoxy group-containing amine compound and the phenoxygroup-containing ammonium salt compound are a compound where the alkylgroup of an amine compound or ammonium salt compound has a phenoxy groupat the terminal opposite the nitrogen atom. The phenoxy group may have asubstituent. Examples of the substituent of the phenoxy group include analkyl group, an alkoxy group, a halogen atom, a cyano group, a nitrogroup, a carboxyl group, a carboxylic acid ester group, a sulfonic acidester group, an aryl group, an aralkyl group, an acyloxy group and anaryloxy group. The substitution site of the substituent may be any of 2-to 6-positions, and the number of substituents may be any in the rangefrom 1 to 5.

The compound preferably has at least one oxyalkylene group between thephenoxy group and the nitrogen atom. The number of oxyalkylene groupswithin the molecule is 1 or more, preferably from 3 to 9, morepreferably from 4 to 6. Among oxyalkylene groups, an oxyethylene group(—CH₂CH₂O—) and an oxypropylene group (—CH(CH₃)CH₂O— or —CH₂CH₂CH₂O—)are preferred, and an oxyethylene group is more preferred.

The sulfonic acid ester group in the sulfonic acid estergroup-containing amine compound and sulfonic acid ester group-containingammonium salt compound may be any of an alkylsulfonic acid ester, acycloalkylsulfonic acid ester and an arylsulfonic acid ester. In thecase of an alkylsulfonic acid ester, the alkyl group preferably has acarbon number of 1 to 20; in the case of a cycloalkylsulfonic acidester, the cycloalkyl group preferably has a carbon number of 3 to 20;and in the case of an arylsulfonic acid ester, the aryl group preferablyhas a carbon number of 6 to 12. The alkylsulfonic acid ester,cycloalkylsulfonic acid ester and arylsulfonic acid ester may have asubstituent, and the substituent is preferably a halogen atom, a cyanogroup, a nitro group, a carboxyl group, a carboxylic acid ester group ora sulfonic acid ester group.

The compound preferably has at least one oxyalkylene group between thesulfonic acid ester group and the nitrogen atom. The number ofoxyalkylene groups within the molecule is 1 or more, preferably from 3to 9, more preferably from 4 to 6. Among oxyalkylene groups, anoxyethylene group (—CH₂CH₂O—) and an oxypropylene group (—CH(CH₃)CH₂O—or —CH₂CH₂CH₂O—) are preferred, and an oxyethylene group is morepreferred.

One of these basic compounds may be used alone, or two or more kindsthereof may be used in combination.

The amount of the basic compound used is usually from 0.001 to 10 mass%, preferably from 0.01 to 5 mass %, based on the solid content of theresist composition.

The ratio of acid generator and basic compound used in the compositionis preferably acid generator/basic compound (by mol)=from 2.5 to 300.That is, the molar ratio is preferably 2.5 or more in view ofsensitivity and resolution and preferably 300 or less from thestandpoint of suppressing the reduction in resolution due to thickeningof the resist pattern with aging after exposure to heat treatment. Theacid generator/basic compound (by mol) is more preferably from 5.0 to200, still more preferably from 7.0 to 150.

[6] Surfactant:

The positive resist composition for immersion exposure of the presentinvention may further contain a surfactant. As for the surfactant, thecomposition preferably contains any one of fluorine-containing and/orsilicon-containing surfactants (a fluorine-containing surfactant, asilicon-containing surfactant and a surfactant containing both afluorine atom and a silicon atom), or two or more kinds thereof.

The amount added of the surfactant is 10 ppm or less, and by setting assuch, the resin (C) having at least either a fluorine atom or a siliconatom can be more unevenly distributed on the surface, whereby the resistfilm surface can be more hydrophobic and in turn, followability of waterat the immersion exposure can be enhanced.

By incorporating the above-described surfactant into the positive resistcomposition for immersion exposure of the present invention, a resistpattern with good performance in terms of sensitivity, resolution andadherence as well as less development defect can be provided when usingan exposure light source of 250 nm or less, particularly 220 nm or less.

Examples of the fluorine-containing and/or silicon-containing surfactantinclude surfactants described in JP-A-62-36663, JP-A-61-226746,JP-A-61-226745, JP-A-62-170950, JP-A-63-34540, JP-A-7-230165,JP-A-8-62834, JP-A-9-54432, JP-A-9-5988, JPA-2002-277862 and U.S. Pat.Nos. 5,405,720, 5,360,692, 5,529,881, 5,296,330, 5,436,098, 5,576,143,5,294,511 and 5,824,451. The following commercially availablesurfactants each may also be used as it is.

Examples of the commercially available surfactant which can be usedinclude a fluorine-containing surfactant and a silicon-containingsurfactant, such as EFtop EF301 and EF303 (produced by Shin-Akita KaseiK.K.); Florad FC430, 431 and 4430 (produced by Sumitomo 3M Inc.);Megaface F171, F173, F176, F189, F113, F110, F177, F120 and R08(produced by Dainippon Ink & Chemicals, Inc.); Surflon S-382, SC101,102, 103, 104, 105 and 106 (produced by Asahi Glass Co., Ltd.); TroysolS-366 (produced by Troy Chemical); GF-300 and OF-150 (produced byToagosei Chemical Industry Co., Ltd.); Surflon S-393 (produced by SeimiChemical Co., Ltd.); EFtop EF121, EF122A, EF122B, RF122C, EF125M,EF135M, EF351, 352, EF801, EF802 and EF601 (produced by JEMCO Inc.);PF636, PF656, PF6320 and PF6520 (produced by OMNOVA); and FTX-204G,208G, 218G, 230G, 204D, 208D, 212D, 218D and 222D (produced by NEOS Co.,Ltd.). In addition, polysiloxane polymer KP-341 (produced by Shin-EtsuChemical Co., Ltd.) may also be used as a silicon-containing surfactant.

Other than these known surfactants, a surfactant using a polymer havinga fluoro-aliphatic group derived from a fluoro-aliphatic compound whichis produced by a telomerization process (also called a telomer process)or an oligomerization process (also called an oligomer process), may beused. The fluoro-aliphatic compound can be synthesized by the methoddescribed in JP-A-2002-90991.

The polymer having a fluoro-aliphatic group is preferably a copolymer ofa fluoro-aliphatic group-containing monomer with a (poly(oxyalkylene))acrylate and/or a (poly(oxyalkylene)) methacrylate, and the polymer mayhave an irregular distribution or may be a block copolymer. Examples ofthe poly(oxyalkylene) group include a poly(oxyethylene) group, apoly(oxypropylene) group and a poly(oxybutylene) group. This group mayalso be a unit having alkylenes differing in the chain length within thesame chain, such as block-linked poly(oxyethylene, oxypropylene andoxyethylene) and block-linked poly(oxyethylene and oxypropylene).Furthermore, the copolymer of a fluoro-aliphatic group-containingmonomer and a (poly(oxyalkylene)) acrylate (or methacrylate) is notlimited only to a binary copolymer but may also be a ternary or greatercopolymer obtained by simultaneously copolymerizing two or moredifferent fluoro-aliphatic group-containing monomers or two or moredifferent (poly(oxyalkylene)) acrylates (or methacrylates).

Examples thereof include, as the commercially available surfactant,Megaface F178, F-470, F-473, F-475, F-476 and F-472 (produced byDainippon Ink & Chemicals, Inc.) and further include a copolymer of aC₆F₁₃ group-containing acrylate (or methacrylate) with a(poly(oxyalkylene)) acrylate (or methacrylate), and a copolymer of aC₃F₇ group-containing acrylate (or methacrylate) with a(poly(oxyethylene)) acrylate (or methacrylate) and a(poly(oxypropylene)) acrylate (or methacrylate).

In the present invention, a surfactant other than thefluorine-containing and/or silicon-containing surfactant may also beused. Specific examples thereof include a nonionic surfactant such aspolyoxyethylene alkyl ethers (e.g., polyoxyethylene lauryl ether,polyoxyethylene stearyl ether, polyoxyethylene cetyl ether,polyoxyethylene oleyl ether), polyoxyethylene alkylaryl ethers (e.g.,polyoxyethylene octylphenol ether, polyoxyethylene nonylphenol ether),polyoxyethylene•polyoxypropylene block copolymers, sorbitan fatty acidesters (e.g., sorbitan monolaurate, sorbitan monopalmitate, sorbitanmonostearate, sorbitan monooleate, sorbitan trioleate, sorbitantristearate), and polyoxyethylene sorbitan fatty acid esters (e.g.,polyoxyethylene sorbitan monolaurate, polyoxyethylene sorbitanmonopalmitate, polyoxyethylene sorbitan monostearate, polyoxyethylenesorbitan trioleate, polyoxyethylene sorbitan tristearate).

One of such surfactants may be used alone, or some of these may be usedin combination.

The amount of the surfactant used is preferably from 0 to 2 mass %, morepreferably from 0.001 to 1 mass %, based on the entire amount of theresist composition (excluding the solvent).

[7] Onium Carboxylate:

The positive resist composition for immersion exposure of the presentinvention may contain an onium carboxylate. Examples of the oniumcarboxylate include sulfonium carboxylate, iodonium carboxylate andammonium carboxylate. In particular, the onium carboxylate is preferablyan iodonium salt or a sulfonium salt. Furthermore, the carboxylateresidue of the onium carboxylate for use in the present inventionpreferably contains no aromatic group and no carbon-carbon double bond.The anion moiety is preferably a linear, branched, monocyclic orpolycyclic alkylcarboxylate anion having a carbon number of 1 to 30,more preferably the carboxylate anion above with the alkyl group beingpartially or entirely fluorine-substituted. The alkyl chain may containan oxygen atom. Thanks to such a construction, the transparency to lightat 220 nm or less is ensured, the sensitivity and resolution areenhanced, and the iso/dense bias and exposure margin are improved.

Examples of the fluorine-substituted carboxylate anion includefluoroacetate, difluoroacetate, trifluoroacetate, pentafluoropropionate,heptafluorobutyrate, nonafluoropentanoate, perfluorododecanoate,perfluorotridecanoate, perfluorocyclohexanecarboxylate and2,2-bistrifluoromethylpropionate anions.

These onium carboxylates can be synthesized by reacting a sulfonium,iodonium or ammonium hydroxide and a carboxylic acid with silver oxidein an appropriate solvent.

The content of the onium carboxylate in the composition is generallyfrom 0.1 to 20 mass %, preferably from 0.5 to 10 mass %, more preferablyfrom 1 to 7 mass %, based on the entire solid content of thecomposition.

[8] Dissolution Inhibiting Compound Capable of Decomposing by the Actionof an Acid to Increase the Solubility in an Alkali Developer and Havinga Molecular Weight of 3,000 or Less

The positive resist composition for immersion exposure of the presentinvention may contain a dissolution inhibiting compound capable ofdecomposing by the action of an acid to increase the solubility in analkali developer and having a molecular weight of 3,000 or less(hereinafter, sometimes referred to as a “dissolution inhibitingcompound”). As the dissolution inhibiting compound, an alicyclic oraliphatic compound containing an acid-decomposable group, such asacid-decomposable group-containing cholic acid derivative described inProceeding of SPIE, 2724, 355 (1996), so as not to reduce thetransparency to light at 220 nm or less is preferred. Examples of theacid-decomposable group and alicyclic structure are the same as thosedescribed above with respect to the resin as the component (B).

In the case where the positive resist composition for immersion exposureof the present invention is exposed by a KrF excimer laser or irradiatedwith an electron beam, the composition preferably contains a structurewhere the phenolic hydroxyl group of a phenol compound is substituted byan acid-decomposable group. The phenol compound is preferably a compoundcontaining from 1 to 9 phenol skeletons, more preferably from 2 to 6phenol skeletons.

The molecular weight of the dissolution inhibiting compound for use inthe present invention is 3,000 or less, preferably from 300 to 3,000,more preferably from 500 to 2,500.

The amount of the dissolution inhibiting compound added is preferablyfrom 3 to 50 mass %, more preferably from 5 to 40 mass %, based on thesolid content of the resist composition.

Specific examples of the dissolution inhibiting compound are set forthbelow, but the present invention is not limited thereto.

Other Additives:

The positive resist composition for immersion exposure of the presentinvention may further contain, for example, a dye, a plasticizer, aphotosensitizer, a light absorber and a compound for acceleratingdissolution in a developer (for example, a phenol compound having amolecular weight of 1,000 or less, or a carboxyl group-containingalicyclic or aliphatic compound), if desired.

The phenol compound having a molecular weight of 1,000 or less can beeasily synthesized by one skilled in the art with reference to themethod described, for example, in JP-A-4-122938, JP-A-2-28531, U.S. Pat.No. 4,916,210 and European Patent 219294.

Specific examples of the carboxyl group-containing alicyclic oraliphatic compound include, but are not limited to, a carboxylic acidderivative having a steroid structure, such as cholic acid, deoxycholicacid and lithocholic acid, an adamantanecarboxylic acid derivative, anadamantanedicarboxylic acid, a cyclohexanecarboxylic acid and acyclohexanedicarboxylic acid.

Pattern Forming Method:

The positive resist composition for immersion exposure of the presentinvention is preferably used in a film thickness of 30 to 250 nm, morepreferably from 30 to 200 nm, from the standpoint of enhancing theresolution. Such a film thickness can be attained by setting the solidcontent concentration in the positive resist composition to anappropriate range, thereby imparting an appropriate viscosity andenhancing the coatability and film-forming property.

The entire solid content concentration in the positive resistcomposition is generally from 1 to 10 mass %, preferably from 1 to 8.0mass %, more preferably from 1.0 to 6.0 mass %.

The positive resist composition for immersion exposure of the presentinvention is used by dissolving the components above in a predeterminedorganic solvent, preferably in the above-described mixed solvent,filtering the solution, and coating it on a predetermined support asfollows. The filter used for filtering is preferably apolytetrafluoroethylene-, polyethylene- or nylon-made filter having apore size of 0.1 μm or less, more preferably 0.05 μm or less, still morepreferably 0.03 μm or less.

For example, the resist composition is coated on such a substrate (e.g.,silicon/silicon dioxide-coated substrate) as used in the production of aprecision integrated circuit device, by an appropriate coating methodsuch as spinner or coater and dried to form a resist film.

The resist film is irradiated with an actinic ray or radiation through apredetermined mask, preferably baked (heated) and then subjected todevelopment and rinsing, whereby a good pattern can be obtained.

Examples of the actinic ray or radiation include infrared light, visiblelight, ultraviolet light, far ultraviolet light, X-ray and electronbeam, but the radiation is preferably far ultraviolet light at awavelength of 250 nm or less, more preferably 220 nm or less, still morepreferably from 1 to 200 nm. Specific examples thereof include KrFexcimer laser light (248 nm), ArF excimer laser light (193 nm), F₂excimer laser light (157 nm), X-ray and electron beam, with ArF excimerlaser light, F₂ excimer laser light, EUV (13 nm) and electron beam beingpreferred.

Before forming the resist film, an antireflection film may be previouslyprovided by coating on the substrate.

The antireflection film used may be either an inorganic film type suchas titanium, titanium dioxide, titanium nitride, chromium oxide, carbonand amorphous silicon, or an organic film type comprising a lightabsorber and a polymer material. Also, the organic antireflection filmmay be a commercially available organic antireflection film such asDUV30 Series and DUV-40 Series produced by Brewer Science, Inc., andAR-2, AR-3 and AR-5 produced by Shipley Co., Ltd.

In the development step, an alkali developer is used as follows. Thealkali developer which can be used to the positive resist compositionfor immersion exposure is an alkaline aqueous solution of, for example,inorganic alkalis such as sodium hydroxide, potassium hydroxide, sodiumcarbonate, sodium silicate, sodium metasilicate and aqueous ammonia,primary amines such as ethylamine and n-propylamine, secondary aminessuch as di ethylamine and di-n-butylamine, tertiary amines such astriethylamine and methyldiethylamine, alcohol amines such asdimethylethanolamine and triethanolamine, quaternary ammonium salts suchas tetramethylammonium hydroxide and tetraethylammonium hydroxide, orcyclic amines such as pyrrole and piperidine.

Furthermore, this alkali developer may be used after adding theretoalcohols and a surfactant each in an appropriate amount.

The alkali concentration of the alkali developer is usually from 0.1 to20 mass %.

The pH of the alkali developer is usually from 10.0 to 15.0.

Also, the above-described alkaline aqueous solution may be used afteradding thereto alcohols and a surfactant each in an appropriate amount.

As for the rinsing solution, pure water is used, and the pure water maybe used after adding thereto a surfactant in an appropriate amount.

After the development or rinsing, a treatment of removing the developeror rinsing solution adhering on the pattern by a supercritical fluid maybe performed.

In the exposure process after forming a film by using the resistcomposition, exposure (immersion exposure) may be performed by filling aliquid (immersion medium) having a refractive index higher than that ofair between the resist film and a lens at the irradiation with anactinic ray or radiation. By this exposure, the resolution can beenhanced. The immersion medium used may be any liquid as long as it hasa refractive index higher than that of air, but pure water is preferred.

The immersion liquid used in the immersion exposure is described below.

The immersion liquid is preferably a liquid being transparent to lightat the exposure wavelength and having as small a temperature coefficientof refractive index as possible so as to minimize the distortion of anoptical image projected on the resist film. Particularly, when theexposure light source is an ArF excimer laser (wavelength: 193 nm),water is preferably used in view of easy availability and easyhandleability in addition to the above-described aspects.

Furthermore, a medium having a refractive index of 1.5 or more can alsobe used from the standpoint that the refractive index can be moreenhanced. This medium may be either an aqueous solution or an organicsolvent.

In the case of using water as the immersion liquid, for the purpose ofdecreasing the surface tension of water and increasing the surfaceactivity, an additive (liquid) which does not dissolve the resist filmon a wafer and at the same time, gives only a negligible effect on theoptical coat at the undersurface of the lens element, may be added in asmall ratio. The additive is preferably an aliphatic alcohol having arefractive index nearly equal to that of water, and specific examplesthereof include methyl alcohol, ethyl alcohol and isopropyl alcohol. Byvirtue of adding an alcohol having a refractive index nearly equal tothat of water, even when the alcohol component in water is evaporatedand its content concentration is changed, the change in the refractiveindex of the entire liquid can be advantageously made very small. On theother hand, if a substance opaque to light at 193 nm or an impuritygreatly differing in the refractive index from water is intermixed, thisincurs distortion of the optical image projected on the resist film.Therefore, the water used is preferably distilled water. Pure waterobtained by further filtering the distilled water through an ionexchange filter or the like may also be used.

The electrical resistance of water is preferably 18.3 MQcm or more, andTOC (total organic carbon) is preferably 20 ppb or less. Also, the wateris preferably subjected to a deaeration treatment.

The lithography performance can be enhanced by raising the refractiveindex of the immersion liquid. From such a standpoint, an additive forraising the refractive index may be added to water, or deuterium water(D₂O) may be used in place of water.

In order to prevent the resist film from directly contacting with theimmersion liquid, an immersion liquid sparingly soluble film(hereinafter, sometimes referred to as a “topcoat”) may be providedbetween the immersion liquid and the resist film formed from thepositive resist composition for immersion exposure of the presentinvention. The functions required of the topcoat are suitability forcoating on the resist upper layer part, transparency to radiationparticularly at 193 nm, and difficult solubility in the immersionliquid. It is preferred that the topcoat does not intermix with theresist and can be uniformly coated on the resist upper layer.

In view of transparency to light at 193 nm, the topcoat is preferably anaromatic-free polymer, and specific examples thereof include ahydrocarbon polymer, an acrylic acid ester polymer, a polymethacrylicacid, a polyacrylic acid, a polyvinyl ether, a silicon-containingpolymer and a fluorine-containing polymer. The resin (C) having at leasteither a fluorine atom or a silicon atom may also be suitable as thetopcoat. If impurities dissolve out into the immersion liquid from thetopcoat, the optical lens is contaminated. For this reason, the residualmonomer components of the polymer are preferably less contained in thetopcoat.

On peeling off the topcoat, a developer may be used or a releasing agentmay be separately used. The releasing agent is preferably a solvent lesspermeating the resist film. From the standpoint that the peeling stepcan be performed simultaneously with the resist development step, thetopcoat is preferably peelable with an alkali developer and for thepeeling with an alkali developer, the topcoat is preferably acidic, butin view of non-intermixing with the resist film, the topcoat may beneutral or alkaline.

With no difference in the refractive index between the topcoat and theimmersion liquid, the resolution is enhanced. In the case of using wateras the immersion liquid at the exposure with an ArF excimer laser(wavelength: 193 nm), the topcoat for ArF immersion exposure preferablyhas a refractive index close to the refractive index of the immersionliquid. From the standpoint of making the refractive index close to thatof the immersion liquid, the topcoat preferably contains a fluorineatom. Also, in view of transparency and refractive index, the topcoat ispreferably a thin film.

The topcoat is preferably free of intermixing with the resist film andfurther with the immersion liquid. From this standpoint, when theimmersion liquid is water, the topcoat solvent is preferably a mediumwhich is sparingly soluble in the resist solvent and is water-insoluble.On the other hand, when the immersion liquid is an organic solvent, thetopcoat may be either water-soluble or water-insoluble.

EXAMPLES

The present invention is described in greater detail below by referringto Examples, but the present invention should not be construed as beinglimited thereto.

Synthesis Example 1 Synthesis of Resin (1)

In a nitrogen stream, 8.6 g of cyclohexanone was charged into athree-neck flask and heated at 80° C. Thereto, a solution obtained bydissolving 8.0 g of norbornane lactone methacrylate, 4.0 g ofdihydroxyadamantyl methacrylate, 9.0 g of 2-adamantyl-isopropylmethacrylate and a polymerization initiator V-601 (produced by Wako PureChemical Industries, Ltd.) in a concentration of 8 mol % based on themonomers, in 70 g of cyclohexanone was added dropwise over 6 hours.After the completion of dropwise addition, the reaction was furtherallowed to proceed at 80° C. for 2 hours. The resulting reactionsolution was left standing to cool and then, added dropwise to a mixedsolution of 800 ml of hexane/200 ml of ethyl acetate over 20 minutes,and the powder precipitated was collected by filtration and dried, as aresult, 17 g of Resin (1) was obtained. The weight average molecularweight of the obtained Resin was 8,500 in terms of standard polystyreneand the polydispersity (Mw/Mn) was 1.8.

Acid-Decomposable Resins (2) to (20) were synthesized in the same manneras in Synthesis Example 1.

Structures of Acid-Decomposable Resins (1) to (20) and the molar ratioof repeating units (from the left in the structural formula), weightaverage molecular weight and polydispersity in each resin are shown inTable 2 below.

TABLE 2 Compositional Ratio Mw/ No. Monomer (1) Monomer (2) Monomer (3)Monomer (4) (by mol) Mw Mn  1

— 50/20/30  8500 1.8  2

— 40/30/30  9000 1.7  3

40/10/40/10  9200 1.7  4

— 50/20/30 10100 1.7  5

— 40/10/50  8700 1.8  6

40/20/30/10  8800 1.8  7

40/10/30/20 10500 1.9  8

40/20/30/10  9600 1.8  9

— 50/10/40  9300 1.9 10

— 50/20/30  9100 2.0 11

40/10/30/20  8000 1.8 12

40/15/40/5  8300 2.0 13

30/20/40/10  8400 1.8 14

— 40/20/40  8100 1.8 15

40/10/25/25  6800 2.0 16

40/10/25/25  8100 1.8 17

— 40/30/30  7800 2.0 18

— 40/30/30  9000 1.7 19

40/10/20/30  9100 2.0 20

— 40/20/40  9600 1.7

Synthesis Example 2 Synthesis of Resin (HR-17)

Hexafluoroisopropyl acrylate (produced by Wako Pure Chemical Industries,Ltd.) (43 g) was dissolved in propylene glycol monomethyl ether acetateto prepare 150 g of a solution having a solid content concentration of20 mass %. To this solution, 8 mmol % (3.68 g) of a polymerizationinitiator, V-601, produced by Wako Pure Chemical Industries, Ltd. wasadded. The resulting solution was added dropwise to 20.0 g of propyleneglycol monomethyl ether acetate heated to 80° C., over 4 hours in anitrogen atmosphere. After the completion of dropwise addition, thereaction solution was stirred for 2 hours to obtain Reaction Solution(1). After the completion of reaction, Reaction Solution (1) was cooledto room temperature and added dropwise to a 20-fold amount of amethanol/water=8/1 mixed solvent. The oily compound separated wasrecovered by decantation to obtain 22 g of the objective Resin (HR-17).

The weight average molecular weight in terms of standard polystyrenedetermined by GPC was 4,400, and the polydispersity was 1.3.

Each resin shown in Resin (C) of Table 3 was synthesized in the samemanner as in Synthesis Example 2.

Examples and Comparative Examples

<Preparation of Resist>

The components shown in Tables below were dissolved in a solvent toprepare a solution having a solid content concentration of 4 mass %, andthe obtained solution was filtered through a polyethylene filter havinga pore size of 0.05 μm to prepare a positive resist solution forimmersion exposure. The resist compositions prepared were evaluated bythe following methods, and the results are shown in the same Tables. Asfor each component in the Tables, when a plurality of species were used,the ratio is a ratio by mass.

The amount added of the resin (C) is mass % based on the entire solidcontent of the resist composition.

[Image Performance Test]

[Exposure Condition]

This condition is to form a resist pattern by an immersion exposuremethod using pure water.

An organic antireflection film, ARC29A (produced by Nissan ChemicalIndustries, Ltd.), was coated on a silicon wafer and baked at 205° C.for 60 seconds to form an antireflection film of 78 nm in thickness, andthe positive resist composition for immersion exposure prepared abovewas coated thereon and baked at 100° C. for 60 seconds to form a resistfilm of 100 nm in thickness. The obtained wafer was subjected to patternexposure using an ArF excimer laser immersion scanner (NA: 1.20). Theimmersion liquid used was ultrapure water. Thereafter, the resist filmwas heated at 100° C. for 60 seconds, developed with an aqueoustetramethylammonium hydroxide solution (2.38 mass %) for 30 seconds,rinsed with pure water and spin-dried to obtain a resist pattern.

[Watermark Defect (WM Defect)]

The exposure dose for reproducing a 1:1 line-and-space mask pattern witha line width of 65 nm was taken as an optimal exposure dose, and thewafer after pattern formation at an optimal exposure dose was evaluatedby a defect inspection apparatus 2360 (manufactured by KLA Tencol K.K.Development defects detected were observed by S9380II (manufactured byHitachi, Ltd.), and the number of WM defects in all development defectswas evaluated.

The sample was rated A when the number of WM defects per wafer (onesheet of a 12-inch wafer) is from 0 to 10, rated B when from 11 to 20,and rated C when more than 20. A smaller number of WM defects indicateshigher suitability for immersion exposure.

[Evaluation of Receding Contact Angle]

The positive resist composition of immersion exposure prepared above wasspin-coated on a silicon wafer and baked on a hot plate to form a 100-nmresist film. The receding contact angle)(°) of a water droplet wasmeasured using a dynamic contact angle meter (manufactured by KyowaInterface Science Co., Ltd.) by an expansion-contraction method. Adroplet having an initial droplet size of 35 μL was suctioned at a rateof 6 μL/sec for 5 seconds at a room temperature of 23±3° C. and ahumidity of 45±5%, and a value when the dynamic contact angle duringsuction was stabilized was taken as the receding contact angle.

TABLE 3 Resin Acid Resin Solvent Basic Receding (A) Generator (C) (ratioby Compound Surfactant Contact WM (2 g) (mg) (mass %) mass) (mg) (mg)Angle (°) Defect Example 1  1 z2 HR-17 SL-1/SL-6 N-1 W-1 74 A (80) (0.3)(95/5) (7) (3) Example 2  2 z80 HR-39 SL-1/SL-2/SL-6 N-2 W-2 75 A (70)(2.0) (60/37/3) (11) (3) Example 3  3 z79 HR-26 SL-1/SL-3/SL-6 N-3 W-373 A (60) (0.7) (70/22/8) (6) (3) Example 4  4 z68 HR-28 SL-1/SL-4/SL-6N-1 W-3 75 A (110) (0.3) (55/40/5) (7) (3) Example 5  5 z66 HR-47SL-4/SL-6 N-1 W-3 75 A (100) (0.4) (90/10) (7) (3) Example 6  1 z2 HR-17SL-1/SL-7 N-1 W-3 76 A (80) (0.3) (95/5) (9) (3) Example 7  2 z80 HR-39SL-1/SL-2/SL-7 N-1 W-3 77 A (70) (2.0) (60/37/3) (7) (3) Example 8  3z79 HR-26 SL-1/SL-3/SL-7 N-1 W-3 76 A (60) (0.7) (70/22/8) (6) (3)Example 9  4 z68 HR-28 SL-1/SL-4/SL-7 N-1 W-3 77 A (110) (0.3) (55/40/5)(7) (3) Example 10  5 z66 HR-47 SL-4/SL-7 N-1 W-3 77 A (100) (0.4)(90/10) (8) (3) Example 11  1 z2 HR-17 SL-1/SL-8 N-1 W-3 71 A (80) (0.3)(95/5) (7) (3) Example 12  2 z80 HR-39 SL-1/SL-2/SL-8 N-1 W-3 72 A (70)(2.0) (60/37/3) (7) (3) Example 13  3 z79 HR-26 SL-1/SL-3/SL-8 N-1 W-370 A (60) (0.7) (70/22/8) (7) (3) Example 14  4 z68 HR-28 SL-1/SL-4/SL-8N-1 W-3 71 A (110) (0.3) (55/40/5) (7) (3) Example 15  5 z66 HR-47SL-4/SL-8 N-1 W-3 72 A (100) (0.4) (90/10) (7) (3) Example 16  6 z2HR-50 SL-1/SL-2/SL-7 N-1 W-1 73 A (80) (2.0) (60/35/5) (7) (3) Example17  7 z80 HR-42 SL-1/SL-2/SL-7 N-2 W-2 76 A (70) (0.5) (60/37/3) (11)(3) Example 18  8 z79 HR-29 SL-1/SL-2/SL-7 N-3 W-3 75 A (60) (0.3)(60/37/3) (6) (3) Example 19  9 z68 HR-24 SL-1/SL-2/SL-7 N-1 W-3 75 A(110) (0.4) (60/37/3) (7) (3) Example 20 10 z66 HR-26 SL-1/SL-2/SL-7 N-1W-3 77 A (100) (0.7) (60/37/3) (7) (3) Example 21 11 z60 HR-39SL-1/SL-2/SL-7 N-1 W-3 76 A (80) (2.0) (60/37/3) (9) (3) Example 22 12z2 HR-47 SL-1/SL-2/SL-7 N-1 W-3 72 A (80) (0.4) (60/37/3) (7) (3)Example 23 13 z2 HR-47 SL-1/SL-2/SL-7 N-1 W-3 74 A (80) (0.4) (60/37/3)(6) (3) Example 24 14 z80 HR-26 SL-1/SL-2/SL-7 N-1 W-3 75 A (70) (0.7)(60/37/3) (7) (3) Example 25 15 z79 HR-47 SL-1/SL-2/SL-7 N-1 W-3 77 A(60) (0.4) (60/37/3) (8) (3) Example 26 16 z68 HR-17 SL-1/SL-2/SL-7 N-1W-3 75 A (110) (0.3) (60/37/3) (7) (3) Example 27 17 z66 HR-39SL-1/SL-2/SL-7 N-1 W-3 73 A (100) (2.0) (60/37/3) (7) (3) Example 28 18z60 HR-26 SL-1/SL-2/SL-7 N-1 W-3 73 A (80) (0.7) (60/37/3) (7) (3)Example 29 19 z2 HR-28 SL-1/SL-2/SL-7 N-1 W-3 74 A (80) (0.3) (60/37/3)(7) (3) Example 30 20 z2 HR-47 SL-1/SL-2/SL-7 N-1 W-3 76 A (80) (0.4)(60/37/3) (7) (3) Example 31  6 z2 HR-50 SL-1/SL-2/SL-6 N-1 W-3 71 A(80) (2.0) (60/37/3) (7) (3) Example 32  7 z2 HR-42 SL-1/SL-2/SL-6 N-1W-3 74 A (80) (0.5) (60/37/3) (7) (3) Example 33  8 z2 HR-29SL-1/SL-2/SL-6 N-1 W-3 74 A (80) (0.3) (60/37/3) (7) (3) Example 34  9z2 HR-24 SL-1/SL-2/SL-6 N-1 W-3 73 A (80) (0.4) (60/37/3) (7) (3)Example 35 10 z2 HR-26 SL-1/SL-2/SL-6 N-1 W-3 75 A (80) (0.7) (60/37/3)(7) (3) Example 36 11 z2 HR-39 SL-1/SL-2/SL-6 N-1 W-3 74 A (80) (2.0)(60/37/3) (7) (3) Example 37 12 z2 HR-47 SL-1/SL-2/SL-6 N-1 W-3 70 A(80) (0.4) (60/37/3) (7) (3) Example 38 13 z2 HR-47 SL-1/SL-2/SL-6 N-1W-3 72 A (80) (0.4) (60/37/3) (7) (3) Example 39 14 z2 HR-26SL-1/SL-2/SL-6 N-1 W-3 72 A (80) (0.7) (60/37/3) (7) (3) Example 40 15z2 HR-47 SL-1/SL-2/SL-6 N-1 W-3 74 A (80) (0.4) (60/37/3) (7) (3)Example 41 16 z2 HR-17 SL-1/SL-2/SL-6 N-1 W-3 74 A (80) (0.3) (60/37/3)(7) (3) Example 42 17 z2 HR-39 SL-1/SL-2/SL-6 N-1 W-3 72 A (80) (2.0)(60/37/3) (7) (3) Example 43 18 z2 HR-26 SL-1/SL-2/SL-6 N-1 W-3 71 A(80) (0.7) (60/37/3) (7) (3) Example 44 19 z2 HR-28 SL-1/SL-2/SL-6 N-1W-3 73 A (80) (0.3) (60/37/3) (7) (3) Example 45 20 z2 HR-47SL-1/SL-2/SL-6 N-1 W-3 74 A (80) (0.4) (60/37/3) (7) (3) Example 46  1z2 HR-17 SL-1/SL-2/SL-6 N-1 W-1 74 A (80) (0.3) (97/1/2) (7) (3) Example47  5 z66 HR-47 SL-4/SL-6 N-1 W-3 71 A (100) (0.4) (85/15) (7) (3)Example 48  5 z66 HR-47 SL-4/SL-7 N-1 W-3 72 A (100) (0.4) (85/15) (8)(3) Resin Acid Resin Solvent Basic Receding (A) Generator (C) (ratio byCompound Surfactant Contact WM (g) (mg) (mass %) mass) (mg) (mg) Angle(°) Defect Example 49 3/4 z80 HR-39 SL-1/SL-2/SL-7 N-1 W-3 76 A (1/1)(70) (2.0) (60/37/3) (7) (3) Example 50 1/7 z68 HR-28 SL-1/SL-4/SL-6 N-1W-3 76 A (1/1) (110) (0.3) (55/40/5) (7) (3) Example 51 3/4 z80 HR-39SL-1/SL-2/SL-7 N-1 — 76 A (1/1) (70) (2.0) (60/37/3) (7) Example 52 1/7z68 HR-28 SL-1/SL-4/SL-6 N-1 — 76 A (1/1) (110) (0.3) (55/40/5) (7)Resin Acid Resin Solvent Basic Receding (A) Generator (C) (ratio byCompound Surfactant Contact WM (2 g) (mg) (mass %) mass) (mg) (mg) Angle(°) Defect Comparative  1 z2 HR-17 SL-1 N-1 W-1 61 C Example 1 (80)(0.3) (100) (7) (3) Comparative  2 z80 HR-39 SL-1/SL-2 N-2 W-3 62 CExample 2 (70) (2.0) (60/40) (8) (3) Comparative  3 z79 HR-26 SL-1/SL-3N-3 W-3 61 C Example 3 (60) (0.7) (70/30) (6) (3) Comparative  4 z68HR-28 SL-1/SL-4 N-1 W-3 62 C Example 4 (110) (0.3) (60/40) (8) (3)Comparative  5 z66 HR-47 SL-4 N-1 W-3 62 C Example 5 (100) (0.4) (100)(8) (3) Comparative  1 z2 HR-17 SL-1/SL-6 N-1 W-3 60 C Example 6 (80)(0.3) (99/1) (8) (3) Comparative  2 z80 HR-39 SL-1/SL-2/SL-7 N-1 W-3 62C Example 7 (70) (2.0) (60/39/1) (8) (3) Comparative  3 z79 HR-26SL-1/SL-3/SL-7 N-1 W-3 60 C Example 8 (60) (0.7) (70/29/1) (8) (3)Comparative  4 z68 HR-28 SL-1/SL-4/SL-7 N-1 W-3 62 C Example 9 (110)(0.3) (55/44/1) (8) (3) Comparative  5 z66 HR-47 SL-4/SL-8 N-1 W-3 62 CExample 10 (100) (0.4) (99/1) (8) (3) Comparative  1 z2 HR-17 SL-1/SL-6N-1 W-3 66 B Example 11 (80) (0.3) (50/50) (8) (3) Comparative  2 z80HR-39 SL-1/SL-2/SL-7 N-1 W-3 65 B Example 12 (70) (2.0) (50/10/40) (8)(3) Comparative  3 z79 HR-26 SL-1/SL-3/SL-7 N-1 W-3 66 B Example 13 (60)(0.7) (50/20/30) (8) (3) Comparative  4 z68 HR-28 SL-1/SL-4/SL-7 N-1 W-367 B Example 14 (110) (0.3) (20/30/50) (8) (3) Comparative  5 z66 HR-47SL-4/SL-8 N-1 W-3 65 B Example 15 (100) (0.4) (75/25) (8) (3)Comparative  1 z2 HR-17 SL-1/SL-4 N-1 W-3 62 C Example 16 (80) (0.3)(95/5) (8) (3) Comparative  2 z80 HR-39 SL-1/SL-2/SL-3 N-1 W-3 62 CExample 17 (70) (2.0) (60/37/3) (8) (3) Comparative  3 z79 HR-26SL-1/SL-3/SL-5 N-1 W-3 61 C Example 18 (60) (0.7) (70/22/8) (8) (3)Comparative  4 z68 HR-28 SL-1/SL-4/SL-4 N-1 W-3 62 C Example 19 (110)(0.3) (55/40/5) (8) (3) Comparative  5 z66 HR-47 SL-4/SL-2 N-1 W-3 62 CExample 20 (100) (0.4) (90/10) (8) (3) Comparative  6 z2 HR-50 SL-1/SL-2N-1 W-1 62 C Example 21 (80) (2.0) (60/40) (7) (3) Comparative  7 z80HR-42 SL-1/SL-2 N-2 W-2 63 C Example 22 (70) (0.5) (60/40) (11) (3)Comparative  8 z79 HR-29 SL-1/SL-2 N-3 W-3 62 C Example 23 (60) (0.3)(60/40) (6) (3) Comparative  9 z68 HR-24 SL-1/SL-2 N-1 W-3 61 C Example24 (110) (0.4) (60/40) (7) (3) Comparative 10 z66 HR-26 SL-1/SL-2 N-1W-3 65 B Example 25 (100) (0.7) (60/40) (7) (3) Comparative 11 z60 HR-39SL-1/SL-2 N-1 W-3 63 C Example 26 (80) (2.0) (60/40) (9) (3) Comparative12 z2 HR-47 SL-1/SL-2 N-1 W-3 61 C Example 27 (80) (0.4) (60/40) (7) (3)Comparative 13 z2 HR-47 SL-1/SL-2 N-1 W-3 60 C Example 28 (80) (0.4)(60/40) (6) (3) Comparative 14 z80 HR-26 SL-1/SL-2 N-1 W-3 61 C Example29 (70) (0.7) (60/40) (7) (3) Comparative 15 z79 HR-47 SL-1/SL-2 N-1 W-362 C Example 30 (60) (0.4) (60/40) (8) (3) Comparative 16 z68 HR-17SL-1/SL-2 N-1 W-3 62 C Example 31 (110) (0.3) (60/40) (7) (3)Comparative 17 z66 HR-39 SL-1/SL-2 N-1 W-3 61 C Example 32 (100) (2.0)(60/40) (7) (3) Comparative 18 z60 HR-26 SL-1/SL-2 N-1 W-3 60 C Example33 (80) (0.7) (60/40) (7) (3) Comparative 19 z2 HR-28 SL-1/SL-2 N-1 W-363 C Example 34 (80) (0.3) (60/40) (7) (3) Comparative 20 z2 HR-47SL-1/SL-2 N-1 W-3 64 C Example 35 (80) (0.4) (60/40) (7) (3) Comparative 6 z2/z40 HR-26 SL-1/SL-6 N-3 W-1 65 B Example 36 (40/120) (1.0) (98/2)(6) (3) The denotations in Tables are as follows. The acid generatorsare corresponding to those described above. N-1: N,N-Dibutylaniline N-2:2,6-Diisopropylaniline N-3: 2-Phenylbenzimidazole W-1: Megaface F176(produced by Dainippon Ink & Chemicals, Inc.) (fluorine-containing) W-2:Troysol S-366 (produced by Troy Chemical) W-3: PF6320 (produced byOMNOVA, fluorine-containing) SL-1: Propylene glycol monomethyl etheracetate (PGMEA) SL-2: Propylene glycol monomethyl ether (PGME) SL-3:Ethyl lactate SL-4: Cyclohexanone SL-5: 2-Heptanone SL-6:γ-Butyrolactone SL-7: Propylene carbonate SL-8: N-methylpyrrolidone

INDUSTRIAL APPLICABILITY

According to the present invention, a positive resist composition forimmersion exposure, ensuring that the receding contact angle forimmersion liquid at the immersion exposure can be more improved and thewatermark (WM) defect can be reduced, and a pattern forming method usingthe same are provided.

This makes it possible to perform scanning at a high speed even in theexposure using a scan-type immersion exposure machine, thereby improvingthe productivity of immersion exposure, and also raise the reliabilitybecause of reduction in the WM defect.

This application is based on Japanese patent application JP 2008-249216,filed on Sep. 26, 2008, the entire content of which is herebyincorporated by reference, the same as if set forth at length.

The invention claimed is:
 1. A positive resist composition for immersionexposure, comprising the following (A) to (D): (A) a resin capable ofdecomposing by an action of an acid to increase a solubility of theresin in an alkali developer; (B) a compound capable of generating anacid upon irradiation with an actinic ray or radiation; (C) a resinhaving at least either one of a fluorine atom and a silicon atom; and(D) a mixed solvent containing at least one kind of a solvent selectedfrom the group consisting of solvents represented by any one of thefollowing formulae (S1) to (S3), in which a total amount of the at leastone kind of the solvent is from 3 to 20 mass % based on all solvents ofthe mixed solvent (D):

wherein each of R₁ to R₇ independently represents an alkyl group, acycloalkyl group or an aryl group; and R₁ and R₂, R₃ and R₄, and R₆ andR₇ may combine with each other to form a ring, respectively, the resin(C) contains at least one group selected from the group consisting ofthe following (x) to (z): (x) an alkali-soluble group, (y) a groupcapable of decomposing by the action of an alkali developer to increasethe solubility in an alkali developer, and (z) a group capable ofdecomposing by the action of an acid, polydispersity of the resin (C) isfrom 1 to 2, the compound (B) is a compound represented by the followingformula (ZI):

wherein R₂₀₂ and R₂₀₃ independently represents an organic group, Z⁻ isan aliphatic sulfonate anion substituted by a fluorine atom at theα-position of the sulfonic acid, and the resin (A) contains at least onerepeating unit represented by formula (1):

wherein R₁ represents a hydrogen atom, a methyl group or a grouprepresented by —CH₂—R₉, and R₉ represents a monovalent organic group, R₂represents an alkyl group or a cycloalkyl group, and each Rindependently represents an atomic group necessary for forming analicyclic structure together with the carbon atom; wherein the resin (C)is an organic polymer.
 2. The positive resist composition for immersionexposure according to claim 1, wherein the resin (A) contains at leasttwo kinds of repeating units represented by formula (1):

wherein R₁ represents a hydrogen atom, a methyl group or a grouprepresented by —CH₂—R₉, and R₉ represents a monovalent organic group, R₂represents an alkyl group or a cycloalkyl group, and each Rindependently represents an atomic group necessary for forming analicyclic structure together with the carbon atom.
 3. The positiveresist composition for immersion exposure according to claim 1, whereinthe resin (A) contains at least one repeating unit represented byformula (1) and at least one repeating unit represented by formula (2):

wherein each of R₁ and R₃ independently represents a hydrogen atom, amethyl group or a group represented by —CH₂—R₉ and R₉ represents amonovalent organic group, each of R₂, R₄, R₅ and R₆ independentlyrepresents an alkyl group or a cycloalkyl group, and each Rindependently represents an atomic group necessary for forming analicyclic structure together with the carbon atom.
 4. The positiveresist composition for immersion exposure according to claim 1, whereinthe resin (A) contains a lactone structure-containing repeating unitrepresented by the following formula (3):

wherein A represents an ester bond (a group represented by —COO—), or agroup represented by —CONH—, R₀ represents, in the case where aplurality of R₀'s are present, each independently represents, analkylene group, a cycloalkylene group or a combination thereof, Zrepresents, in the case where a plurality of Z's are present, eachindependently represents, an ether bond, an ester bond, an amide bond, aurethane bond or a urea bond, R₈ represents a monovalent organic grouphaving a lactone structure, n is a repetition number of the structurerepresented by —R₀—Z— in the repeating unit represented by formula (3)and represents an integer of 1 to 5, and R₇ represents a hydrogen atom,a halogen atom or an alkyl group.
 5. The positive resist composition forimmersion exposure according to claim 1, wherein the aliphatic sulfonateanion in the compound (B) is substituted by a monovalent group having apolycyclic cycloalkyl group.
 6. The positive resist composition forimmersion exposure according to claim 1, wherein the resin (C) contains(x) an alkali-soluble group.
 7. The positive resist composition forimmersion exposure according to claim 1, wherein the resin (C) contains(y) a group capable of decomposing by the action of an alkali developerto increase the solubility in an alkali developer.
 8. The positiveresist composition for immersion exposure according to claim 1, whereinthe resin (C) contains (z) a group capable of decomposing by the actionof an acid.
 9. The positive resist composition for immersion exposureaccording to claim 1, wherein the amount added of the resin (C) is in anamount of 0.01 to 10 mass %, based on the entire solid content of theresist composition.
 10. The positive resist composition for immersionexposure according to claim 1, wherein the composition further containsan onium carboxylate.
 11. The positive resist composition for immersionexposure according to claim 1, wherein the mixed solvent (D) furthercontains cyclohexanone.
 12. The positive resist composition forimmersion exposure according to claim 1, wherein the resin (C) containsa carbon atom in the backbone chain.
 13. The positive resist compositionfor immersion exposure according to claim 1, wherein, in the resin (C),the backbone chain is constituted by only a carbon atom.
 14. Thepositive resist composition for immersion exposure according to claim 1,wherein the resin (C) contains at least one repeating unit derived froma monomer selected from the group consisting of (meth)acrylic acid,styrene, ethylene, norbornene, and derivatives thereof.
 15. The positiveresist composition for immersion exposure according to claim 1, whereinthe resin (C) contains a repeating unit derived from a (meth)acrylicacid derivative, and the repeating unit contains at least one offluorine atom or silicon atom in the side chain.
 16. The positive resistcomposition for immersion exposure according to claim 1, wherein theresin (C) contains a repeating unit derived from a (meth)acrylic acidderivative, and the repeating unit contains fluorine atom in the sidechain.
 17. The positive resist composition for immersion exposureaccording to claim 1, wherein the resin (C) only consists of a repeatingunit derived from a monomer selected from the group consisting of(meth)acrylic acid, styrene, ethylene, norbornene, and derivativesthereof.
 18. A positive resist composition for immersion exposure,comprising the following (A) to (D): (A) a resin capable of decomposingby an action of an acid to increase a solubility of the resin in analkali developer; (B) a compound capable of generating an acid uponirradiation with an actinic ray or radiation; (C) a resin having atleast either one of a fluorine atom and a silicon atom; and (D) a mixedsolvent containing at least one kind of a solvent selected from thegroup consisting of solvents represented by any one of the followingformulae (S1) to (S3), in which a total amount of the at least one kindof the solvent is from 3 to 20 mass % based on all solvents of the mixedsolvent (D):

wherein each of R₁ to R₇ independently represents an alkyl group, acycloalkyl group or an aryl group; and R₁ and R₂, R₃ and R₄, and R₆ andR₇ may combine with each other to form a ring, respectively, the resin(C) contains at least one group selected from the group consisting ofthe following (x) to (z): (x) an alkali-soluble group, (y) a groupcapable of decomposing by the action of an alkali developer to increasethe solubility in an alkali developer, and (z) a group capable ofdecomposing by the action of an acid, and the mixed solvent (D) furthercontains at least one selected from the group consisting of ethyllactate, cyclohexanone and 2-heptanone.
 19. The positive resistcomposition for immersion exposure according to claim 18, wherein themixed solvent (D) further contains propylene glycol monomethyl etheracetate.
 20. The positive resist composition for immersion exposureaccording to claim 18, wherein the mixed solvent (D) containsγ-butyrolactone as the solvent represented by formula (S2).
 21. Thepositive resist composition for immersion exposure according to claim18, wherein the mixed solvent (D) contains cyclohexanone.
 22. A positiveresist composition for immersion exposure, comprising the following (A)to (D): (A) a resin capable of decomposing by an action of an acid toincrease a solubility of the resin in an alkali developer; (B) acompound capable of generating an acid upon irradiation with an actinicray or radiation; (C) a resin having at least either one of a fluorineatom and a silicon atom; and (D) a mixed solvent containing at least onekind of a solvent selected from the group consisting of solventsrepresented by any one of the following formulae (S1) to (S3), in whicha total amount of the at least one kind of the solvent is from 3 to 20mass % based on all solvents of the mixed solvent (D):

wherein each of R₁ to R₇ independently represents an alkyl group, acycloalkyl group or an aryl group; and R₁ and R₂, R₃ and R₄, and R₆ andR₇ may combine with each other to form a ring, respectively, the resin(C) contains at least one group selected from the group consisting ofthe following (x) to (z): (x) an alkali-soluble group, (y) a groupcapable of decomposing by the action of an alkali developer to increasethe solubility in an alkali developer, and (z) a group capable ofdecomposing by the action of an acid, and the compound (B) is a compoundrepresented by the following formula (I):

wherein X⁺ represents an organic counter ion, and R represents ahydrogen atom or an organic group.
 23. The positive resist compositionfor immersion exposure according to claim 22, wherein the organic groupof R is an organic group represented by the following formula (II):—(CH₂)_(n)—Rc-(Y)_(m)  (II) wherein Rc represents a monocyclic orpolycyclic organic group having a carbon number of 3 to 30 which maycontain a cyclic ether, cyclic thioether, cyclic ketone, cycliccarbonate ester, lactone or lactam structure, Y represents a hydroxylgroup, a halogen atom, a cyano group, a carboxyl group, a hydrocarbongroup having a carbon number of 1 to 10, a hydroxyalkyl group having acarbon number of 1 to 10, an alkoxy group having a carbon number of 1 to10, an acyl group having a carbon number of 1 to 10, an alkoxycarbonylgroup having a carbon number of 2 to 10, an acyloxy group having acarbon number of 2 to 10, an alkoxyalkyl group having a carbon number of2 to 10, or an alkyl halide group having a carbon number of 1 to 8;m=from 0 to 6; when a plurality of Y's are present, each Y may be thesame as or different from every other Y, and n=from 0 to
 10. 24. Thepositive resist composition for immersion exposure according to claim23, wherein Rc in formula (II) is a polycyclic organic group.
 25. Thepositive resist composition for immersion exposure according to claim23, wherein Rc in formula (II) is an adamantyl group.
 26. A resist filmformed by coating a resist composition on a substrate and drying thecoated resist composition, the resist composition comprising thefollowing (A) to (D): (A) a resin capable of decomposing by an action ofan acid to increase a solubility of the resin in an alkali developer;(B) a compound capable of generating an acid upon irradiation with anactinic ray or radiation; (C) a resin having at least either one of afluorine atom and a silicon atom; and (D) a mixed solvent containing atleast one kind of a solvent selected from the group consisting ofsolvents represented by any one of the following formulae (S1) to (S3),in which a total amount of the at least one kind of the solvent is from3 to 20 mass % based on all solvents of the mixed solvent (D):

wherein each of R₁ to R₇ independently represents an alkyl group, acycloalkyl group or an aryl group; and R₁ and R₂, R₃ and R₄, and R₆ andR₇ may combine with each other to form a ring, respectively, the resin(C) contains at least one group selected from the group consisting ofthe following (x) to (z): (x) an alkali-soluble group, (y) a groupcapable of decomposing by the action of an alkali developer to increasethe solubility in an alkali developer, and (z) a group capable ofdecomposing by the action of an acid, and the mixed solvent (D) furthercontains at least one selected from the group consisting of ethyllactate, cyclohexanone and 2-heptanone.
 27. A resist film formed bycoating a resist composition on a substrate and drying the coated resistcomposition, the resist composition comprising the following (A) to (D):(A) a resin capable of decomposing by an action of an acid to increase asolubility of the resin in an alkali developer; (B) a compound capableof generating an acid upon irradiation with an actinic ray or radiation;(C) a resin having at least either one of a fluorine atom and a siliconatom; and (D) a mixed solvent containing at least one kind of a solventselected from the group consisting of solvents represented by any one ofthe following formulae (S1) to (S3), in which a total amount of the atleast one kind of the solvent is from 3 to 20 mass % based on allsolvents of the mixed solvent (D):

wherein each of R₁ to R₇ independently represents an alkyl group, acycloalkyl group or an aryl group; and R₁ and R₂, R₃ and R₄, and R₆ andR₇ may combine with each other to form a ring, respectively, the resin(C) contains at least one group selected from the group consisting ofthe following (x) to (z): (x) an alkali-soluble group, (y) a groupcapable of decomposing by the action of an alkali developer to increasethe solubility in an alkali developer, and (z) a group capable ofdecomposing by the action of an acid, and the compound (B) is a compoundrepresented by the following formula (I):

wherein X⁺ represents an organic counter ion, and R represents ahydrogen atom or an organic group.